CN1064061C

CN1064061C - Novel resin composition

Info

Publication number: CN1064061C
Application number: CN94194681A
Authority: CN
Inventors: 名取至; 今泉公夫; 加藤清雄
Original assignee: Asahi Kasei Kogyo KK
Current assignee: Asahi Kasei Corp
Priority date: 1994-02-01
Filing date: 1994-11-21
Publication date: 2001-04-04
Anticipated expiration: 2014-11-21
Also published as: EP0743341A4; JP3102440B2; KR0174806B1; CN1051320C; CN1139447A; EP0743325A1; CA2178742A1; CA2178609A1; CA2178742C; CN1139438A; DE69434993D1; WO1995021202A1; EP0743325B1; CA2178609C; US5830965A; EP0743325A4; US5883192A; EP0743341A1; DE69434935D1; WO1995021217A1

Abstract

Disclosed is a resin composition comprising ( alpha ) at least one polymer selected from the group consisting of a non-modified cyclic monomer unit-containing polymer and a modified cyclic monomer unit-containing polymer having a number average molecular weight of from 10,000 to 5,000,000, wherein the cyclic monomer unit is derived from a cyclic conjugated diene, and ( beta ) at least one polymer other than the polymer ( alpha ), and wherein the polymer ( alpha ) is present in an amount of at least 1 % by weight, based on the total weight of the polymers ( alpha ) and ( beta ). The molecular structure of the polymer ( alpha ) which is contained in the novel resin composition of the present invention and which is selected from a non-modified cyclic monomer unit-containing polymer and a modified cyclic monomer unit-containing polymer, wherein the cyclic monomer unit is derived from a cyclic conjugated diene, can be controlled with large freedom. Therefore by combining the polymer ( alpha ) with a polymer ( beta ) other than the polymer ( alpha ), a resin composition which is excellent in various properties, such as theremal stability with respect to rigidity, and impact resistance can be provided with large freedom with respect to the choice of its properties.

Description

Novel resin composition

The present invention relates to a novel resin composition comprising a polymer containing a cyclic monomer unit, more specifically, the present invention relates to a novel resin composition comprising (α) at least one polymer selected from the group consisting of a polymer containing an unmodified cyclic monomer unit and a polymer containing a modified cyclic monomer unit, and (β) at least one polymer other than the polymer (α), which has excellent thermal properties, such as thermal stability (with respect to rigidity), and mechanical properties, such as impact resistance.

In recent years, polymer chemistry has been advancing through various innovations in order to meet the ever-increasing diversity of commercial needs. Especially in the field of polymers used as commercially important materials, extensive and intensive research has been conducted on developing polymers having excellent thermal and mechanical properties. Various proposals have been made for such polymers and for their production.

The polymer material has advantages in that it is light in weight, has a great freedom of choice in terms of the shape of the final molded product, and exhibits many unique characteristics according to the type of polymer material used. Therefore, the polymer material can be used in an extremely wide range of application fields, such as automobile parts, electronic and electric parts, rail parts, aerospace parts, fibers, clothing, medical equipment parts, packaging materials for medicines and foods, and materials for general miscellaneous goods. In addition, the importance of polymers is increasing and developing rapidly in accordance with the diversity of commercial demands and technological progress.

In recent years, in the field of materials used, such as automobile parts, electronic and electric parts, and the like, there has been an increasing demand for reducing the number of kinds of materials required to reduce the weight and number of parts, because of environmental concerns. To meet this requirement, extensive research has been conducted on how to replace structural non-polymeric materials with polymeric materials and how to reduce the number of types of structural materials.

However, one of the important problems that must be solved as a means of developing polymer materials, particularly organic polymer materials widely used as structural materials, is a problem inherent in conventional polymer materials, that is, the mechanical properties of polymer materials greatly change according to changes in ambient temperature.

The reason why the above phenomenon occurs in the conventional polymer material is assumed as follows. When the ambient temperature of the polymer material is raised to a temperature higher than the glass transition temperature (Tg) of the polymer material, the molecular chains of the polymer are transformed from a glassy state to a rubbery state, and this change in state becomes a major cause of considerable change in mechanical properties. Therefore, in the case of using a polymer of a single molecular structure, sucha problem has not been solved in principle so far, and thus extensive and intensive studies have been made to solve the problem using a combination of a plurality of different types of polymer materials.

For example, in order to obtain a polymer material which not only improves mechanical properties such as thermal stability with respect to rigidity and mechanical strength, impact resistance and dimensional stability but also is unlikely to be adversely changed at ambient temperature, it has been attempted to use a combination of one polymer and another polymer different from the polymer in glass transition temperature (Tg) to obtain a composite polymer material, or to copolymerize plural types of monomers, thereby producing a polymer material composed of copolymer chains having segments different in glass transition temperature.

Examples of such conventional techniques include the following methods:

polymers having a higher melting temperature (Tm), but not having a satisfactorily high Tg [ e.g. Polyamide (PA), Polyester (PES), polyphenylene sulfide (PPS), polyacetal (e.g. polyoxymethylene, POM) or polypropylene (PP)]are used together with another polymer having a higher Tg [ e.g. polyphenylene ether (PPE), Polycarbonate (PC), Polyacrylate (PAR), Polysulfone (PSF), Polyetherketone (PEK), Polyetheretherketone (PEEK), Liquid Crystalline Polyester (LCP) or polystyrene (PSt)], to give a polymer material having improved thermal stability with respect to stiffness;

polymers which do not have a satisfactorily low Tg, such as Polyamides (PA), Polyesters (PEs), polyphenylene sulfides (PPS), polyacetals such as Polyoxymethylene (POM), polypropylene (PP), polyphenylene ether (PPE) or polystyrene (PSt), and polymers having a lower Tg such as ethylene-propylene rubber (EPR), ethylene-propylene-diene terpolymer (EPDM), styrene-butadiene rubber (SBR), hydrogenated styrene-butadiene rubber (styrene-ethylene-butylene-styrene (SEBS), styrene-isoprene rubber (SIR), hydrogenated styrene-isoprene rubber, Butadiene Rubber (BR), Isoprene Rubber (IR), Chloroprene Rubber (CR), nitrile rubber (acrylonitrile-butadiene rubber, NBR), ethylene-containing ionomers, acrylic rubbers, silicone rubber, fluororubber, polyamide elastomer or polyester elastomer, thereby obtaining a polymer material improved in impact resistance;

polymers such as polystyrene (PSt), styrene-butadiene rubber (SBR), hydrogenated styrene-butadiene rubber (SEBS), styrene-isoprene rubber (SIR), hydrogenated styrene-isoprene rubber, ABS resin or AES resin are used together with a higher Tg polymer, resulting in a polymer material modified in thermal stability with respect to mechanical strength; and

aromatic or alicyclic cyclic monomer units are introduced into polymer molecular chains [ e.g., Polyamide (PA), Polyester (PEs), polypropylene (PP), or Polyethylene (PE)]by copolymerization, thereby obtaining a polymer material improved in thermal stability in terms of rigidity, mechanical strength, and the like. Of these, several methods have been commercially available.

However, in these conventional techniques, each type of different polymer to be used in combination or each type of monomer and comonomer to be used in combination must be largely changed depending on the characteristics to be improved. Therefore, these conventional methods do not always meet the market trend that requires a reduction in the number of types of structural materials required.

As a solution to this problem, (hydrogenated) conjugated diene polymers have been proposed. The conjugated diene polymer can be prepared by living anionic polymerization, and therefore the conjugated diene polymer has a large degree of freedom in terms of molecular chain design, and it is quite easy to control the characteristics of the conjugated diene polymer to be obtained, for example, by copolymerization. Therefore, it can be predicted that, when a conjugated diene polymer, for example, of which copolymerization properties are appropriately controlled, is used as a modifier for a polymer material, various properties, such as thermal stability, impact resistance and dimensional stability in terms of rigidity and mechanical strength, can be imparted to the polymer material very arbitrarily. Therefore, intensive studies have been made on the development of a conjugated diene polymer as a representative modifier for composite resin materials.

Representative examples of known conjugated diene polymers include homopolymers such as polybutadiene and polyisoprene, copolymers of block, graft, ladder and random configurations such as butadiene-isoprene copolymer, styrene-butadiene copolymer, propylene-butadiene copolymer, styrene-isoprene copolymer, α -methylstyrene-butadiene copolymer, α -methylstyrene-isoprene copolymer, acrylonitrile-butadiene copolymer, acrylonitrile-isoprene copolymer, butadiene-methyl methacrylate copolymer and isoprene-methyl methacrylate copolymer, and hydrogenated polymers derived therefrom.

For example, in the field of thermoplastic elastomers, when a conjugated diene polymer in the form of a thermoplastic elastomer is used as a modifier to modify the impact resistance of a polymeric material, a conjugated diene block copolymer has been conventionally used which comprises a polymer chain composed of an agglomerated phase (i.e., a polymer block having a Tg higher than room temperature) and an elastomeric phase (i.e., a polymer block having a Tg lower than room temperature).

Representative examples of such block copolymers are styrene-butadiene (isoprene) -styrene block copolymers and hydrogenated products thereof.

Further, for improving various properties (such as heat resistance, flowability and adhesion) of a styrene-butadiene (isoprene) -styrene block copolymer or a hydrogenated product thereof, it has been widely practiced to use the block copolymer or the hydrogenated product thereof in the form of a block copolymer composition obtained by blending the above-mentioned block copolymer or the hydrogenated product thereof with another polymer such as polystyrene, polyolefin, polyphenylene ether or a styrene-butadiene diblock copolymer or a hydrogenated product thereof.

On the other hand, various proposals have been made as to a method for producing a conjugated diene polymer, which is also important from a commercial viewpoint.

In particular, various studies have been made on the development of a polymerization catalyst capable of providing a conjugated diene polymer having a high cis-1, 4-bond content, with the object of obtaining a conjugated diene polymer having improved thermal and mechanical properties.

For example, a catalyst system mainly composed of an alkali metal such as lithium or sodium compound and a composite catalyst system mainly composed of a transition metal such as nickel, cobalt or iron compound have been proposed. Some such catalyst systems have been used for commercial scale polymerization of butadiene, isoprene, and the like (see, e.g., ingend. chem., 48, 784(1956) and examined japanese patent application publication 37-8193).

On the other hand, in order to obtain a conjugated diene polymer having a further increased cis-1, 4-bond content and to provide a catalyst having a further improved polymerization activity, a great deal of research has been conducted on a composite catalyst system composed of a rare earth metal compound and an organometallic compound containing a metal belonging to group I, II or III of the periodic Table. Inaddition, along with the study of such catalyst systems, highly stereospecific polymerizations have also been intensively studied [ see, for example, j.polym.sci., polym.chem.ed., 18, 3345 (1980); sci, sinica, 2/3, 734 (1980); chem. suppl, 4, 61 (1981); german patent application 2, 848, 964; rubber chem. technol., 58, 117 (1985).

Among these composite catalyst systems, it has been confirmed that a composite catalyst composed mainly of a neodymium compound and an organoaluminum compound not only can provide a desired polymer having a high cis-1, 4-bond content but also has excellent polymerization activity. Therefore, such composite catalysts have been commercially used as catalysts for polymerizing butadiene or the like [ see, for example, angelw.makromol.chem., 94, 119 (1981); macromolecules, 15, 230(1982)].

However, in light of the recent remarkable progress in the art, there is a strong demand for the development of polymer materials having further improved properties, particularly excellent thermal properties (such as melting temperature, glass transition temperature and heat distortion temperature) and excellent mechanical properties (such as tensile modulus and flexural modulus).

As one of the most practical means for satisfying this requirement, there has been attempted to develop a technique of improving the main molecular chain structure of a polymer of a conjugated diene monomer (not only homopolymerizing or copolymerizing a monomer having a smaller steric hindrance, such as butadiene or isoprene, but also a monomer having a large steric hindrance, such as a cyclic conjugated diene monomer, and optionally hydrogenating the resulting conjugated diene polymer to thereby form a cycloolefin monomer unit in the molecular chain) so as to obtain a polymer having excellent thermal characteristics (e.g., thermal stability with respect to rigidity and mechanical strength), excellent impactresistance, such as excellent dimensional stability. Further, it has also been attempted to use these conjugated diene polymers together with other polymers to obtain a composite resin material having improved characteristics.

For homopolymerization or copolymerization of monomers having less steric hindrance, such as butadiene or isoprene, a catalyst system having a satisfactory polymerization activity to some extent has been successfully developed. However, a catalyst system having satisfactory polymerization activity in homopolymerizing or copolymerizing a monomer having large steric hindrance, such as a cyclic conjugated diene monomer, has not been developed so far.

That is, it is difficult even to homopolymerize a cyclic conjugated diene by the conventional technique, and thus a homopolymer having a desired high molecular weight cannot be obtained. Moreover, the copolymerization of a cyclic conjugated diene with a monomer other than said cyclic conjugated diene, with the aim of obtaining optimum thermal and mechanical properties in order to satisfy the various industrial requirements, has also not succeeded as a result, the product obtained being only a low molecular weight oligomer.

In addition, the carbon-carbon double bonds in the cyclic conjugated diene monomer units of the conjugated diene polymer have a large steric hindrance. Therefore, a serious problem in the conventional art is that when it is attempted to introduce cyclic olefin monomer units into the molecular chain of the conjugated diene polymer by a hydrogenation reaction method, the rate of the hydrogenation reaction is considerably low, so that it is extremely difficult to introduce cyclic olefin monomer units into the conjugated diene polymer.

As can be seen from the above, it has not been possible in any conventional technique to obtain a commercially satisfactory polymer containing cyclic conjugated diene monomer units and/or cyclic olefin monomer units.

Therefore, it is highly desired to develop a polymer containing a cyclic monomer unit.

J.am.chem.soc., 81, 448(1959) discloses a cyclohexadiene homopolymer obtained by polymerizing 1, 3-cyclohexadiene (a typical example of cyclic conjugated dienes) using a composite catalyst composed of titanium tetrachloride and triisobutylaluminum, and a polymerization method thereof.

However, the polymerization process disclosed in this prior art document has the disadvantage that a large amount of catalyst has to be used and the polymerization has to be carried out for a long time and the polymers obtained have only a very low molecular weight. Therefore, the polymers obtained with the techniques of this prior art document are of no commercial value. Furthermore, this prior art document does not describe or suggest a method of introducing cycloolefin monomer units into a main molecular chain of a polymer to obtain a novel polymer and a method of providing a composite resin material using such a novel polymer containing cycloolefin monomer units as a component.

J.polym.sci.pt.a, 2, 3277(1964) discloses a process for producing cyclohexadiene homopolymers wherein the 1, 3-cyclohexadiene polymerization is carried out by different polymerization methods, such as free radical polymerization, cationic polymerization, anionic polymerization and coordination polymerization.

However, all the processes disclosed in this prior art document lead to polymers having only very low molecular weights. Thus, the polymers obtained by the techniques of this prior art document are of no commercial value. Further, this prior art document does not describe or suggest a method of introducing cycloolefin monomer units into a polymer molecular chain to obtain a novel polymer and a method of providing a composite resin material using such a novel polymer containing cycloolefin monomer units as a component.

British patent application 1, 042, 625 discloses a process for the production of cyclohexadiene homopolymers wherein the polymerization of 1, 3-cyclohexadiene is carried out using a large amount of an organolithium compound as catalyst.

In the polymerization process disclosed in british patent application 1, 042, 625, the amount of catalyst has to be as high as 1-2 wt.%, based on the total weight of the monomers. Therefore, this method is economically disadvantageous. Furthermore, the polymers obtained by this process have only a very low molecular weight.

In addition, the process of this prior art document has the disadvantage that the polymer obtained contains a large amount of catalyst residues, which are difficult to remove from the polymer, and the polymer obtained by this process is therefore of no commercial value.

Furthermore, this prior art document does not describe or suggest a method of introducing cycloolefin monomer units into the main molecular chain of a polymer to obtain a novel polymer and a method of providing a composite resin material using such a novel polymer containing cycloolefin monomer units as a component.

J.polym.sci., pt.a 3, 1553(1965) discloses a cyclohexadiene homopolymer obtained by polymerizing 1, 3-cyclohexadiene using an organolithium compound as a catalyst. In this prior art document, the polymerization reaction must be continued for up to 5 weeks, and not only does this result in a polymer having a number average molecular weight of only 20,000 or less.

Furthermore, this prior art document does not describe or suggest a method of introducing cycloolefin monomer units into the main molecular chain of a polymer to obtain a novelpolymer and a method of providing a composite resin material using such a novel polymer containing cycloolefin monomer units as a component.

Polym.Prepr. (Amer.chem.Soc., div.Polym.chem.12, 402(1971) states that when 1, 3-cyclohexadiene is polymerized using an organolithium compound as a catalyst, the upper limit of the number average molecular weight of the cyclohexadiene homopolymer obtained is only 10,000 to 15,000.

Furthermore, this prior art document does not describe or suggest a method of introducing cycloolefin monomer units into the main molecular chain of a polymer to obtain a novel polymer and a method of providing a composite resin material using such a novel polymer containing cycloolefin monomer units as a component. Die Makromolekulare Chemie, 163, 13(1973) discloses a cyclohexadiene homopolymer obtained by polymerizing 1, 3-cyclohexadiene using a large amount of an organolithium compound catalyst. However, the polymers obtained with this prior art document are oligomers having a number average molecular weight of only 6, 500.

European Polymer J.9, 895(1973) discloses a copolymer obtained by copolymerizing 1, 3-cyclohexadiene with butadiene and/or isoprene using a π -allylnickel compound as a polymerization catalyst.

However, the polymer obtained with this prior art document is an oligomer of very low molecular weight. Furthermore, it is reported that the polymers of this prior art document have a single glass transition temperature, which means that the polymers have a random copolymer structure.

Kobunshi Ronbun-shu (Collection of the second connecting poly-mer) volume 34, No. 5, 333(1977) discloses a process for the synthesis of alternating copolymers of 1, 3-cyclohexadiene and acrylonitrile using zinc chloride as the polymerization catalyst. However, the alternating copolymers contained in this prior art document are oligomers of very low molecular weight.

J, polym.sci., polym.chem.ed., 20, 901(1982) discloses a cyclohexadiene homopolymer obtained by polymerizing 1, 3-cyclohexadiene using an organic sodium compound as a catalyst. In this prior art document, the organic sodium compound used is sodium naphthalene and the radical anion derived from sodium naphthalene forms a dianion which acts as a polymer initiation site.

This means that although the cyclohexadiene homopolymer reported in this document has an apparent number average molecular weight of 38,700, this homopolymer is actually only a combination of two polymeric molecular chains each having a number average molecular weight of 19,350, respectively, extending from the polymerization initiation site in two different directions.

In addition, in the polymerization method disclosed in this document, the polymerization reaction needs to be carried out at an extremely low temperature. Therefore, the technical content of this prior art document is of no commercial value.

Makromol. chem., 191, 2743(1990) discloses a process for polymerizing 1, 3-cyclohexadiene using polystyryllithium as the polymerization initiator. In this prior art document it is described that not only the transfer reaction by the lithium cations at the end of the proposed polymer takes place simultaneously with the polymerization reaction, but also a strong lithium hydroxide removal reaction takes place. Further, it has been reported that even when polymerization is carried out using polystyrene-based lithium as a polymerization initiator, a styrene-cyclohexadiene block copolymer is not obtained at room temperature, and the obtained product is a cyclohexadiene homopolymer and has a very low molecular weight.

Furthermore, block copolymers of cyclohexadiene and alkaconjugated diene monomers, multiblock copolymers containing at least three blocks of cyclohexadiene polymer blocks and radial block copolymers containing cyclohexadiene polymer blocks are not described or suggested in this prior art document.

As can be readily seen fromthe above, any conventional techniques cannot obtain a polymer containing a monomer unit derived from a cyclic conjugated diene monomer and an excellent resin composition containing such a polymer, which can be satisfactorily used as industrial materials.

Under the circumstances, the present inventors have made an effort to develop a novel cyclic conjugated diene polymer, i.e., a polymer comprising at least one cyclic conjugated diene monomer unit, or comprising at least one cyclic conjugated diene monomer unit and a monomer unit derived from at least one other monomer than the above cyclic conjugated diene monomer, which is copolymerizable with the cyclic conjugated diene monomer, wherein the cyclic conjugated diene polymer has a high number average molecular weight, as a result of which it has not only excellent thermal properties such as in terms of melting temperature, glass transition temperature and heat distortion temperature but also excellent mechanical properties such as high tensile modulus and high flexural modulus; and a method for producing such an excellent cyclic conjugated diene polymer have been extensively and intensively studied. As a result, the present inventors have succeeded in developing a novel polymerization catalyst for producing the above-mentioned polymer, which catalyst has excellent catalytic activity, not only achieves a desired high degree of polymerization, but also enables active anionic polymerization to be efficiently and economically carried out, thereby block-copolymerizing a cyclic conjugated diene monomer and at least one other monomer copolymerizable with the cyclic conjugated diene monomer. With this novel polymerization catalyst, a novel cyclic conjugated diene polymer which has never been reported can be synthesized for the first time. In addition, a technique for obtaining a cyclic conjugated diene polymer has been developed in which monomer units derived from a cyclic conjugated diene monomer are introduced ina desired ratio and in a desired configuration as part or all of the monomer units constituting the main chain of the polymer (see PCT/JP 94/00822). Further, the present inventors have made further studies and as a result, have developed a technique for producing a polymer containing a saturated cyclic monomer unit, which is derived from the above-mentioned cyclic conjugated diene polymer (see PCT/JP 94/00973).

The inventor also makes further research, and as a result, the inventor finds that: by mixing a polymer containing the above cyclic monomer unit derived from a cyclic conjugated diene with at least one polymer other than the polymer containing the cyclic monomer unit, a resin composition free to be improved in terms of thermal and mechanical properties, for example, thermal stability with respect to rigidity and impact resistance can be provided. It is based on this new finding that the present invention has been completed.

Accordingly, it is a main object of the present invention to provide a novel resin composition comprising at least one polymer selected from the group consisting of a polymer containing an unmodified cyclic monomer unit and a polymer containing a modified cyclic monomer unit, wherein the cyclic monomer unit is derived from a cyclic conjugated diene, and at least one polymer other than the above-mentioned polymer derived from a cyclic conjugated diene, which resin composition is advantageous in that not only the resin composition has excellent thermal stability (in terms of rigidity) and mechanical properties (such as impact resistance), but also the thermal and mechanical properties of the resin composition can be freely adjusted.

The foregoing and other objects, advantages and features of the invention will be apparent from the following detailed description and claims taken in conjunction with the accompanying drawings.

In the drawings:

FIG. 1 is a Transmission Electron Microscope (TEM) photograph (. times.5000) of the resin composition of the present invention obtained in example 3;

FIG. 2 is a viscoelastic spectrum of the resin composition of the present invention obtained in example 12;

FIG. 3 is a viscoelastic spectrum of the resin composition of the present invention obtained in example 13; and

FIG. 4 is a diagram of the viscoelastic spectrum of the well-known PA66 (nylon 66) used in examples 12 and 13.

In the present invention, there is provided a resin composition comprising:

(α) at least one polymer selected from the group consisting of a polymer (1) containing an unmodified cyclic monomer unit and a polymer (1 ') containing a modified cyclic monomer unit, the polymer (1) and the polymer (1 ') being represented by the following formulae (1) and (1 '), respectively:

wherein A to F are monomer units constituting the main chain of each of the polymers (1) and (1'), wherein the monomer units A to F are arranged in an arbitrary order, and a to F are the weight percentages of the monomer units A to F based on the total weight of the monomer units A to F, respectively; wherein

Each A is independently selected from the group consisting of cyclic olefin monomeric units,

each B is independently selected from cyclic conjugated diene monomer units,

each C is independently selected from the group consisting of alkaconjugated diene monomer units,

each D is independently selected from vinyl aromatic monomer units,

each E is independently selected from polar monomer units, and

each F is independently selected from ethylene monomer units and α -olefin monomer units, wherein:

a-f meet the following requirements:

a+b+c+d+e+f=100，

0≤a，b≤100，

c is 0. ltoreq. d, e, f<100, and

a + b is not equal to 0; wherein each modifying group S-X, which may be the same or different, is independently a functional group containing at least one member selected from the group consisting of oxygen, nitrogen, sulfur, silicon, phosphorus and halogens including fluorine, chlorine, bromine and iodine or an organic compound residue containing the functional group; and wherein S-X are each the weight percentage of modifying groups S-X by weight of the polymer (1'), and the following requirements are satisfied:

0<s + t + u + v + w + x<100, and

0. ltoreq. s, t, u, v, w, x<100, the number-average molecular weight of the polymer (α) being from 10,000 to 5,000,000, and

(β) at least one polymer other than polymer (α),

the polymer (α) is present in an amount of at least 1wt.%, based on the total weight of polymer (α) and polymer (β).

The following lists basic features and various embodiments of the invention in order to facilitate the understanding of the invention.

1. A resin composition comprising:

(α) at least one polymer selected from the group consisting of a polymer (1) containing an unmodified cyclic monomer unit and a polymer (1 ') containing a modified cyclic monomer unit, the polymer (1) and the polymer (1 ') being represented by the following formulae (1) and (1 '), respectively:wherein A to F are monomer units constituting the main chain of each of the polymers (1) and (1'), wherein the monomer units A to F are arranged in an arbitrary order, and a to F are the weight percentages of the monomer units A to F based on the total weight of the monomer units A to F, respectively; wherein

each B is independently selected from cyclic conjugated diene monomer units,

each D is independently selected from vinyl aromatic monomer units,

each E is independently selected from polar monomer units, and

a-f meet the following requirements:

a+b+c+d+e+f=100，

0≤a，b≤100，

c is 0. ltoreq. d, e, f<100, and

a + b is not equal to 0; wherein each modifying group S-X, which may be the same or different, is independently a functional group containing at least one member selected from the group consisting of oxygen, nitrogen, sulfur, silicon, phosphorus and halogens including fluorine, chlorine, bromine and iodine or an organic compound residue containing the functional group; and wherein S-X are each the weight percentage of modifying groups S-X byweight of the polymer (1'), and the following requirements are satisfied:

0<s + t + u + v + w + x<100, and

(β) at least one polymer other than polymer (α),

2. The resin composition according to the above clause 1, wherein in at least one of the formulae (1) and (1'), a = 100.

3. The resin composition according to the above clause 1, wherein in at least one of the formulae (1) and (1'), b = 100.

4. The resin composition according to the above clause 1, wherein in at least one of the formulae (1) and (1'), a + b =100 and a>0.

5. A resin composition according to item 1 above, wherein in at least one of the formulae (1) and (1'), 0<a + b<100.

6. The resin composition according to item 1 above, wherein in at least one of the formulae (1) and (1'), the main chain has a random copolymer configuration.

7. The resin composition according to item 1 above, wherein in at least one of the formulae (1) and (1'), the main chain has an alternating copolymer configuration.

8. The resin composition according to the above clause 1, wherein in at least one of the formulae (1) and (1'), the main chain has a block copolymer configuration in which the block copolymer has at least one polymer block containing at least one monomer unit selected from the group consisting of A monomer units and B monomer units.

9. The resin composition according to the above clause 1, wherein in at least one of the formulae (1) and (1'), the main chain has a block copolymer configuration in which the block copolymer has at least one polymer block composed of at least one A monomer unit and at least one B monomer unit.

10. The resin composition according to the above clause 1, wherein in at least one of the formulae (1) and (1'), the main chain has a block copolymer configuration in which the block copolymer has at least one polymer block composed of A monomer units.

11. The resin composition according to the above clause 1, wherein in at least one of the formulae (1) and (1'), the main chain has a block copolymer configuration in which the block copolymer has at least one polymer block composed of B monomer units.

12. The resin composition according to any one of the above items 1 to 11, wherein in at least one of the formulae (1) and (1'), the A monomer unit is selected from cycloolefin monomer units represented by the following formula (2):

wherein each R¹Independently represents a hydrogen atom, a halogen atom, C₁-C₂₀Alkyl radical, C₂-C₂₀Unsaturated aliphatic hydrocarbon group, C₅-C₂₀Aryl radical, C₃-C₂₀Cycloalkyl radical, C₄-C₂₀A cycloalkadienyl group or a 5-to 10-membered heterocyclic group containing at least one nitrogen, oxygen or sulfur atom as a heteroatom, x is an integer of 1 to 4, and each R²Independently represents a hydrogen atom, a halogen atom, C₁-C₂₀Alkyl radical, C₂-C₂₀Unsaturated aliphatic hydrocarbon group, C₅-C₂₀Aryl radical, C₃-C₂₀Cycloalkyl radical, C₄-C₂₀Cycloalkadienyl radicals or having at least one nitrogen, oxygen or sulfur atom asA 5-to 10-membered heterocyclic group of a heteroatom, or each R²Independently represents a bond or a group such that two R²Together form the formula A bridge of the formula, wherein R³Definition of (A) and R¹And y is an integer of 1 to 10, and in at least one of (1) and (1'), the B monomer unit is selected from cyclic conjugated diene monomer units represented by the following formula (3):wherein each R¹，R²And x is as defined in formula (2).

13. The polymer according to the above paragraph 12, wherein in at least one of the formulae (1) and (1'), the A monomer unit is selected from cycloolefin monomer units represented by the following formula (4):wherein each R²As defined in formula (2), and wherein in at least one of formulae (1) and (1'), the B monomer units are selected from cyclic conjugated diene monomer units represented by the following formula (5):wherein each R²Defined by formula (2).

14. The resin composition according to any one of the above clauses 1 to 11, wherein each S to X is independently a functional group which is at least one member selected from the group consisting of a hydroxyl group, an ether group, an epoxy group, a carboxylic acid group, an ester group, a carboxylate group, an acid anhydride group, an acid halide group, an aldehyde group, a carbonyl group, an amino group, an amide group, an imide group, an imino group, an oxazoline group, a hydrazine group, a hydrazide group, an amidine group, a nitrile group, a nitro group, an isocyano group, a cyanato group, a silyl ester group, a silyl ether group, a silanol group, a thiol group, a thioether group, a thiocarboxylic acid group, a dithiocarboxylic acid group, a sulfonic acid group, a sulfinic acid group, a sulfenic acid group, a thiocyanate group, an isothiocyanato group, a thioaldehyde group, a thioketo group, a phosphoric acid group, a phosphonic acid group, and a phosphinic.

15. The resin composition according to any one of the above clauses 1 to 11, wherein each S to X is independently a functional group which is at least one member selected from the group consisting of a hydroxyl group, an epoxy group, a carboxylic acid group, an ester group, a carboxylic acid ester group, an acid anhydride group, an amino group, an amide group, an imide group, an imino group, an oxazoline group, a hydrazine group, a hydrazide group, an isocyano group, a cyanato group, an isocyano group, a silyl ester group, a silyl ether group, a silanol group, a thiol group, a thioether group, a thiocarboxylic group and a sulfonic acid group, or a residue of an organic compound containing the functional group.

16. The resin composition according to any one of above clauses 1 to 11, wherein the polymer (β) is a thermoplastic resin.

17. The resin composition according to any one of above clauses 1-11, wherein the polymer (β) is a curable resin.

18. The resin composition according to clause 16, wherein the thermoplastic resin is at least one polymer selected from the group consisting of olefin polymers, styrene polymers, conjugated diene polymers, hydrogenated conjugated diene polymers, (meth) acrylate polymers, (meth) acrylonitrile polymers, halogenated vinyl polymers, ester polymers, ether polymers, amide polymers, imide polymers, thioether polymers, sulfone polymers and ketone polymers.

19. The resin composition according to clause 16, wherein the thermoplastic resin is at least one polymer selected from the group consisting of olefin polymers, styrene polymers, conjugated diene polymers, halogenated conjugated diene polymers, ester polymers, ether polymers, amide polymers and thioether polymers.

20. The resin composition according to any one of the above clauses 1 to 11, wherein the polymer (α) comprises a polymer (1') containing a modified cyclic monomer unit, wherein at least one modifying group of S to X is a functional group selected from a hydroxyl group, an epoxy group, a carboxylic acid group, an ester group, a carboxylate group, an acid anhydride group, an amino group, an amide group, an imide group, an imino group, an oxazoline group, an isocyano group, a cyanato group, an isocyano group, a silyl ester group, a silyl ether group, a silanol group, a thiol group, a thioether group, a thiocarboxylic acid group and a sulfonic acid group, or a residue of an organic compound containing the functional group;

wherein (β) comprises at least one polymer selected from the group consisting of ester polymers containing at least one functional group selected from the group consisting of hydroxyl groups, carboxyl groups, and ester groups, ether polymers containing at least one functional group selected from the group consisting of hydroxyl groups and ether groups, amide polymers containing at least one functional group selected from the group consisting of amino groups, carboxyl groups, and amide groups, and thioether polymers containing at least one functional group selected from the group consisting of thiol groups and thioether groups, and

wherein the resin composition comprises the reaction product of 0.001 to 100 wt.%, based on the weight of the resin composition, of the polymer (α) and the polymer (β), wherein the reaction product is formed by reacting at least one functional group or organic compound residue of the polymer (α) with at least one functional group of the polymer (β).

21. The resin composition according to any one of the above clauses 1 to 11, wherein the polymer (α) comprises a polymer (1') containing a modified cyclic monomer unit, wherein at least one modifying group of S to X is a functional group selected from a hydroxyl group, an epoxy group, a carboxylic acid group, an ester group, a carboxylate group, an acid anhydride group, an amino group, an amide group, an imide group, an imino group, an oxazoline group, an isocyano group, a cyanato group, an isocyano group, a silyl ester group, a silyl ether group, a silanol group, a thiol group, a thioether group, a thiocarboxylic acid group and a sulfonic acid group, or a residue of an organic compound containing the functional group;

wherein the polymer (β) comprises at least one modified polymer selected from the group consisting of a modified olefin polymer, a modified styrene polymer, a modified conjugated diene polymer, a modified hydrogenated conjugated diene polymer, a modified ether polymer and a modified thioether polymer, the at least one modified polymer having at least one functional group or an organic compound residue containing the functional group, wherein the functional group is selected from the group consisting of a hydroxyl group, an epoxy group, a carboxylic acid group, an ester group, a carboxylate group, an acid anhydride group, an amino group, an amide group, an imide group, an imino group, an oxazoline group, an isocyano group, a cyanato group, an isocyanato group, a silyl ester group, a silyl ether group, a silanol group, a thiol group, a thioether group, a thiocarboxylic acid group and a sulfonic acid group, and

wherein the resin composition comprises a reaction product of 0.001 to 100 wt.%, based on the weight of the resin composition, of the polymer (α) and the polymer (β), wherein the reaction product is formed by reacting at least one functional group or organic compound residue of the polymer (α) with at least one functional group or organic compound residue of the polymer (β).

22. A resin composition according to clause 16, wherein the thermoplastic resin is an olefin polymer having an intrinsic viscosity of 0.1 to 100 (L/g) as measured in decalin at 135 ℃.

23. The resin composition according to item 16 above, wherein the thermoplastic resin is a thermoplastic resin having a hydrogen content of 96% H at 25 ℃₂SO₄An amide polymer having an intrinsic viscosity of 0.1 to 100 (liter/g) as measured in (1).

24. The resin composition according to paragraph 16 above, wherein the thermoplastic resin is at least one olefin polymer selected from the group consisting of an ethylene homopolymer, an α -olefin homopolymer and a copolymer of ethylene and α -olefin.

25. A resin composition according to the above paragraph 16, wherein the thermoplastic resin is a crystalline polyamide obtained by polymerizing at least one member selected from the group consisting of a reaction product of a diamine and a dicarboxylic acid, a lactam and an amino acid.

In the present invention, the monomer units of the polymer are named according to nomenclature, thereby adopting the name of the original monomer (from which the monomer unit is derived) attached to the term "unit" as such. For example, the term "cycloolefin monomer unit" means a monomer unit formed in a polymer obtained by polymerizing a cycloolefin monomer, and its molecular structure is such that a cycloalkane corresponding to the cycloolefin monomer is bonded at two carbon atoms of its skeleton. Further, the term "cyclic conjugated diene monomer unit" means a monomer unit formed in a polymer obtained by polymerizing a cyclic conjugated diene monomer, and its molecular structure is such that a cycloolefin corresponding to the cyclic conjugated diene monomer is bonded at two carbon atoms of its skeleton.

In the present invention, at least one polymer selected from the group consisting of the polymer (1) containing an unmodified cyclic monomer unit and the polymer (1 ') containing a modified cyclic monomer unit may be used as the polymer (α). The polymers (1) and (1') each comprise a copolymer composed of a part or all of cyclic olefin monomer units and/or cyclic conjugated diene monomer unitsAnd polymers (1) and (1 ') are represented by the following formulae (1) and (1'), respectively:

wherein A-F, a-F, S-X and S-X are as defined above.

In the present invention, in the case where a plurality of monomer units are contained in the main chain of the polymer chain, the monomer units A to F in the formula (1) or (1') may be the same or different.

In the present invention, it is preferred that each of the polymer (1') containing an unmodified cyclic monomer unit (1) and a modified cyclic monomer unit is a polymer comprising a main chain partially or entirely composed of 5 to 8-membered cyclic olefin monomer units and/or 5 to 8-membered cyclic conjugated diene monomer units, wherein the monomer units are bonded by 1, 2-bonds and/or 1, 4-bonds.

In the present invention, it is preferred that the polymer (α) has a ratio of 1, 2-bonds to 1, 4-bonds of 99/1-1/99, more preferably 90/10-10/90.

In the present invention, the cycloolefin monomer unit is at least one selected from the group consisting of cycloolefin monomer units having a carbocyclic ring structure. Preferably, the cyclic olefin monomer unit is at least one selected from the group consisting of cyclic olefin monomer units having a 5-to 8-membered carbocyclic ring structure. It is particularly preferred that the cycloolefin monomer unit is at least one member selected from the group consisting of cycloolefin monomer units having a 6-membered carbocyclic ring structure.

Examples of cyclic olefin monomeric units include cyclopentane, cyclohexane, cyclooctane, and derivatives thereof. Among them, cyclohexane and its derivatives are particularly preferable.

It is preferable that the cycloolefin monomer unit is a molecular unit represented by the following formula (2):

wherein each R¹Independently represents a hydrogen atom, a halogen atom, C₁-C₂₀Alkyl radical, C₂-C₂₀Unsaturated aliphatic hydrocarbon group, C₅-C₂₀Aryl radical, C₃-C₂₀Cycloalkyl radical, C₄-C₂₀A cycloalkadienyl group or a 5-to 10-membered heterocyclic group having at least one nitrogen, oxygen or sulfur atom as a heteroatom, and x is an integer of 1 to 4, and each R²Independently represents a hydrogen atom, a halogen atom, C₁-C₂₀Alkyl radical, C₂-C₂₀Unsaturated aliphatic hydrocarbon group, C₅-C₂₀Aryl radical, C₃-C₂₀Cycloalkyl radical, C₄-C₂₀Cycloalkadienyl or 5-to 10-membered heterocyclyl having at least one nitrogen, oxygen or sulfur atom as heteroatom, or each R²Independently represents a bond or a group such that two R²Together form formula- A bridge of formula (I) wherein R³Definition of (A) and R¹And y is an integer from 1 to 10.

Most preferably, the cycloolefin monomer unit is a molecular unit represented by the following formula (4):

wherein each R²As defined in formula (2).

In the present invention, the cyclic conjugated diene monomer unit is at least one selected from cyclic conjugated diene monomer units having a carbocyclic ring structure. Preferably, the cyclic conjugated diene monomer unit is at least one selected from cyclic conjugated diene monomer units having a 5-to 8-membered carbocyclic ring structure. It is particularly preferable that the cyclic conjugated diene monomer unit is at least one selected from cyclic conjugated diene monomer units having a 6-membered carbocyclic ring structure.

Examples of cyclic conjugated diene monomer units are cyclopentene, cyclohexene, cyclooctene, and derivatives thereof. Among them, cyclohexene and derivatives thereof are particularly preferable.

More preferably, the cyclic conjugated diene monomer unit is a monomer unit represented by the following formula (3):

wherein each R¹，R²And x is defined as formula (2).

Most preferably, the cyclic conjugated diene monomer unit is a monomer unit represented by the following formula (5):wherein each R²As defined by formula (II).

In the polymer (α) used in the resin composition of the present invention, the sum of the content (a) of cycloolefin monomer units and the content (b) of cyclic conjugated diene monomer units is not particularly limited, and the total content (a + b) may vary depending on the intended use of the resin composition as long as a and b satisfy the relationship of 0<a + b ≦ 100, however, the total content (a + b) is generally in the range of 0.001 to 100 wt.%, preferably 0.01 to 100 wt.%, more preferably 0.1 to 100 wt.%.

Furthermore, in order to obtain the resin composition of the present invention that can be used in the field where the resin composition is required to have high thermal and mechanical properties, it is recommended that the content (a) of the cycloolefin monomer units in the polymer (α) is 1 to 100 wt.%, more preferably 2 to 100 wt.%, optimally 5 to 500 wt.% (based on the total weight of the monomer units a to F of the polymer (α)).

There is no particular limitation on the method for producing the polymer (α) used in the present invention, as long as the polymer (α) contains cycloolefin monomer units and/or cyclic conjugated diene monomer units and has a number average molecular weight falling within the range specified in the present invention.

Further, in the present invention, there is no particular limitation on the method of forming the molecular chain of the polymer (α) containing cycloolefin monomer units.

Examples of such methods include the following:

polymerizing a cyclic conjugated diene monomer to obtain a cyclic conjugated diene homopolymer, and subjecting the resulting cyclic conjugated diene homopolymer to an addition reaction, such as a hydrogenation reaction, at carbon-carbon double bonds in a part or all of cyclic conjugated diene monomer units contained in the cyclic conjugated diene homopolymer to convert the cyclic conjugated diene monomer units into cyclic olefin monomer units;

polymerizing a cyclic conjugated diene monomer and a comonomer copolymerizable therewith to obtain a cyclic conjugated diene copolymer, and subjecting the resulting cyclic conjugated diene copolymer to an addition reaction at carbon-carbon double bonds in a part or all of the cyclic conjugated diene monomer units contained in the cyclic conjugated diene copolymer to convert the cyclic conjugated diene monomer units into cycloolefin monomer units;

polymerizing a cycloolefin monomer with a comonomer to obtain a copolymer containing cycloolefin monomer units;

polymerizing a cycloolefin monomer to obtain a homopolymer containing cycloolefin monomer units; or

Polymerizing a cyclic conjugated diene monomer with a cyclic olefin monomer to obtain a copolymer containing cyclic olefin monomer units. From these methods, a preferred method can be selected as appropriate according to the situation involved.

When the polymer (α) used in the present invention is obtained by a method comprising homopolymerizing or copolymerizing a cyclic conjugated diene monomer to obtain a cyclic conjugated diene polymer and then hydrogenating it, the degree of hydrogenation, i.e., the hydrogenation ratio (mol%) of the carbon-carbon double bonds contained in the cyclic conjugated diene monomer units in the cyclic conjugated diene polymer is not particularly limited and may vary depending on the intended use thereof and depending on the amount of the cycloolefin monomer units required for the modified polymer, however, the degree of hydrogenation is usually 1 to 100 mol%, preferably 5 to 100 mol%, more preferably 10 to 100 mol%, particularly preferably 20 to 100 mol%.

Further, particularly when the resin composition of the present invention is used in the field requiring high thermal and mechanical properties of the polymer, it is recommended that the degree of hydrogenation of the polymer (α) is 50 to 100 mol%, more preferably 70 to 100 mol%, most preferably not less than 90 mol%.

When the resin composition of the present invention is used as an industrial material such as a structural material, the polymer (α) of the resin composition generally has a number average molecular weight of 10,000 to 5,000,000 from the viewpoint of productivity in commercial scale production of such a polymer, it is recommended that the number average molecular weight of the polymer (α) is 15,000 to 5,000,000, preferably 20,000 to 3,000,000, more preferably 25,000 to 2,000,000, particularly preferably 30,000 to 1,000,000, and the most preferable range is 40,000 to 500,000.

When the number average molecular weight of such a polymer is less than 10,000, the polymer is likely to be a solid or viscous liquid which is remarkably brittle, and therefore the commercial value of the polymer as an industrial material becomes extremely low.

On the other hand, when the number average molecular weight of such a modified polymer is higher than 5,000,000, the polymer has disadvantages in many respects from the commercial viewpoint. For example, such a high molecular weight polymer has disadvantages in that it takes a long time to carry out the polymerization reaction, and the melt viscosity of the resulting polymer becomes high.

When the main chain of the polymer (α) used in the present invention is a cyclic conjugated diene homopolymer, it is preferable that the number average molecular weight of the polymer is 40,000 to 5,000,000. when the number average molecular weight of such a modified polymer is less than 40,000, the polymer is likely to become significantly brittle, and therefore the polymer becomes extremely low as a structural material and in commercial value.

From the viewpoint of productivity in producing such a polymer on a commercial scale, the number average molecular weight of the polymer is preferably 40,000 to 3,000,000, more preferably 40,000 to 2,000,000, further preferably 40,000 to 1,000,000. The optimum range for use as a component of the resin composition is 40,000-500,000.

When the main chain of the polymer (α) used in the present invention is a polymer composed of only cycloolefin monomer units or a copolymer composed of only at least one cycloolefin monomer unit and at least one cyclic conjugated diene monomer unit, the number average molecular weight of the polymer is 10,000 to 5,000,000.

From the viewpoint of productivity in producing such a polymer on a commercial scale, the number average molecular weight of the polymer is preferably 15,000 to 5,000,000, more preferably 20,000 to 3,000,000, more preferably 25,000 to 2,000,000, particularly preferably 30,000 to 1,000,000. The most preferred range for the polymer to be used as a component of the resin composition is 40,000-500,000.

When the number average molecular weight of such a polymer is less than 10,000, the polymer is likely to become a significantly brittle solid substance or viscous liquid, and therefore, the commercial value of the modified polymer as a structural material becomes extremely low.

On the other hand, when the number average molecular weight of such a polymer is higher than 5,000,000, the polymer has disadvantages in many respects from the commercial viewpoint. For example, a polymer having such a high molecular weight has a disadvantage in that the polymerization reaction takes a long time and the melt viscosity of the resulting polymer becomes high.

When the main chain of the polymer (α) used in the present invention is a copolymer comprising at least one cyclic conjugated diene monomer unit and at least one monomer unit derived from a monomer copolymerizable with the cyclic conjugated diene monomer, the number average molecular weight of such a polymer is preferably 25,000 to 5,000,000, more preferably 25,000 to 3,000,000, even more preferably 25,000 to 2,000,000, even more preferably 30,000 to 1,000,000.

When the main chain of the polymer (α) used in the present invention is a copolymer comprising at least one cycloolefin monomer unit and at least one monomer unit derived from a monomer copolymerizable with the cycloolefin monomer, the number average molecular weight is 10,000 to 5,000,000. from the viewpoint of productivity in producing such a copolymer on a commercial scale, the number average molecular weight of the copolymer is preferably 15,000 to 5,000,000, more preferably 20,000 to 3,000,000, still more preferably 25,000 to 2,000,000, still more preferably 30,000 to 1,000,000.

When the number average molecular weight of such a copolymer is less than 10,000, the copolymer is likely to be a solid substance or a viscous liquid which is significantly brittle, and therefore the commercial value of the copolymer as an industrial material becomes low.

On the other hand, when the number average molecular weight of such a copolymer is higher than 5,000,000, the copolymer has disadvantages in many respects from the commercial viewpoint. For example, the copolymer having such a high molecular weight has disadvantages in that it takes a long time to perform the polymerization reaction, and the melt viscosity of the copolymer becomes high.

When the main chain of the polymer (α) used in the present invention is a copolymer composed of at least one cycloolefin monomer unit, at least one cyclic conjugated diene monomer unit, and at least one monomer unit derived from a monomer copolymerizable with the cycloolefin monomer and/or the cyclic conjugated diene monomer, the number average molecular weight is 10,000 to 5,000,000.

From the viewpoint of producing such a copolymer on a commercial scale, the number average molecular weight of the copolymer is preferably 15,000 to 5,000,000, more preferably 20,000 to 3,000,000, further preferably 25,000 to 2,000,000, particularly preferably 30,000 to 1,000,000. For the copolymer to be used as the resin composition, the most preferable range is 40,000-500,000.

When the number average molecular weight of such a copolymer is less than 10,000, the copolymer is likely to be a significantly brittle solid substance or viscous liquid, and thus the commercial value of the copolymer as an industrial material becomes extremely low.

On the other hand, when the number average molecular weight of such a copolymer is higher than 5,000,000, the copolymer has disadvantages in many respects from the commercial viewpoint. For example, such a high molecular weight copolymer has disadvantages in that it takes a long time to perform the polymerization reaction, and the melt viscosity of the resulting copolymer becomes high.

When the main chain of the polymer (α) used in the present invention is a block copolymer having at least one polymer block comprising at least one monomer unit selected from the group consisting of cycloolefin monomer units and cyclic conjugated diene monomer units and optionally at least one monomer unit derived from a monomer copolymerizable with the cycloolefin monomer and/or the cyclic conjugated diene monomer, it is preferable that the block copolymer is an at least triblock copolymer having a number average molecular weight of 10,000 to 5,000,000. from the viewpoint of productivity in producing such a block copolymer on a commercial scale, the number average molecular weight of the block copolymer is preferably 15,000 to 5,000,000, more preferably 20,000 to 3,000,000, further preferably 25,000 to 2,000,000, still further preferably 30,000 to 1,000,000.

When the number average molecular weight of such a block copolymer is less than 10,000, the copolymer is likely to be a significantly brittle solid substance or viscous liquid, and thus the commercial value of the copolymer as an industrial material becomes low.

On the other hand, when the number average molecular weight of such a copolymer is higher than 5,000,000, the block copolymer has disadvantages in many respects from the commercial viewpoint. For example, such a high molecular weight block copolymer has disadvantages in that it takes a long time to perform the polymerization reaction, and the melt viscosity of the resulting block copolymer becomes high.

In the present invention, the number average molecular weight

And weight average molecular weightWas determined according to gel permeation chromatography using a calibration curve obtained with reference to standard polystyrene samples.

Of polymers

The value (molecular weight distribution index) is 1.01 to 10, preferably 1.03 to 7.0, more preferably 1.05 to 5.0.

Preferred examples of the polymer containing an unmodified cyclic monomer unit for use in the present invention include those obtained by hydrogenating a polymer alone, such as a homopolymer of a cyclic conjugated diene monomer, a copolymer of at least two different types of cyclic conjugated diene monomers, and a copolymer of a cyclic conjugated diene monomer and a monomer copolymerizable with the cyclic conjugated diene monomer, in which hydrogenation is performed on one or more carbon-carbon double bonds of part or all of the cyclic conjugated diene monomer to convert part or all of the cyclic conjugated diene monomer units into cyclic olefin monomer units.

On the other hand, preferred examples of the modified cyclic monomer unit-containing polymer used in the present invention include those obtained by hydrogenating the above-mentioned preferred unmodified cyclic monomer unit alone with an active agent to bond a functional group or a functional group-containing organic compound residue to such an unmodified polymer.

The unmodified cyclic monomer unit-containing polymer used in the present invention is described in more detail below.

The unmodified cyclic monomer unit-containing polymer used in the present invention includes a polymer having a main chain partially or entirely composed of at least one monomer unit selected from the group consisting of a cycloolefin monomer unit and a cyclic conjugated diene monomer unit.

For example, preferable examples of the polymer containing an unmodified cyclic monomer unit used in the present invention include a homopolymer obtained by polymerizing a cyclic conjugated diene monomer alone, a copolymer obtained by copolymerizing a cyclic conjugated diene monomer and a monomer copolymerizable with the cyclic conjugated diene monomer, and hydrogenation products of these homopolymers and copolymers.

Representative examples of the unmodified cyclic monomer unit-containing polymer used in the present invention include polymers having monomer units derived from only a cyclic conjugated diene monomer, and polymers having monomer units derived from a cyclic conjugated diene monomer and a monomer copolymerizable with the cyclic conjugated diene monomer, and hydrogenation products of these polymers.

More specific examples of the polymer containing an unmodified cyclic monomer unit used in the present invention include a homopolymer of a single cyclic conjugated diene monomer, a copolymer of at least two different cyclic conjugated diene monomers, and a copolymer of a cyclic conjugated diene monomer and a monomer copolymerizable with the cyclic conjugated diene monomer, and hydrogenation products ofthese homopolymers and copolymers.

The cyclic conjugated diene monomer in the present invention preferably has at least a 5-membered carbocyclic ring structure.

More preferably, the cyclic conjugated diene monomer of the present invention has a 5-to 8-membered carbocyclic ring structure, particularly a 6-membered carbocyclic ring structure.

That is, preferred examples of the unmodified cyclic monomer unit-containing polymer used in the present invention include those in which the main chain is partially or entirely composed of at least one monomer unit selected from the group consisting of a cycloolefin monomer unit having a cyclohexane ring and a cyclic conjugated diene monomer unit having a cyclohexene ring.

Specific examples of the cyclic conjugated diene monomer are 1, 3-cyclopentadiene, 1, 3-cyclohexadiene, 1, 3-cyclooctadiene, and derivatives thereof. Preferred examples of the cyclic conjugated diene monomer are 1, 3-cyclohexadiene and 1, 3-cyclohexadiene derivatives. Among them, 1, 3-cyclohexadiene is most preferable.

In the present invention, examples of the monomer copolymerizable with the cyclic conjugated diene monomer include known polymerizable monomers.

Examples of such copolymerizable monomers include chain conjugated diene monomers such as 1, 3-butadiene, isoprene, 2, 3-dimethyl-1, 3-butadiene, 1, 3-pentadiene and 1, 3-hexadiene, vinyl aromatic monomers such as styrene, α -methylstyrene, o-methylstyrene, p-tert-butylstyrene, 1, 3-dimethylstyrene, divinylbenzene, vinylnaphthalene, diphenylethylene and vinylpyridine, polar vinyl monomers such as methyl methacrylate, methyl acrylate, acrylonitrile, methyl vinyl ketone and α -methyl cyanoacrylate, polar monomers such as ethylene oxide, propylene oxide, lactones, lactams and cyclosiloxanes, ethylene and α -olefin, which may be used alone or in combination.

When the unmodified cyclic monomer-containing polymer used in the present invention is a copolymer, such copolymer may have any configuration depending on the intended use of the copolymer.

For example, the copolymer can be a block copolymer, such as a diblock copolymer, a triblock copolymer, a tetrablock copolymer, a multiblock copolymer that is an at least pentablock copolymer, as well as a radial block copolymer, a graft copolymer, a ladder copolymer, a random copolymer, or an alternating copolymer.

In the unmodified cyclic monomer-containing polymer used in the present invention, the monomer unit derived from a comonomer copolymerizable with the cycloolefin monomer or the cyclic conjugated diene monomer may be a monomer unit formed by post-polymerization treatment such as hydrogenation.

In the best mode of the process for producing the cyclic conjugated diene polymer used in the present invention, the polymer can be prepared by living anionic polymerization, and thus the molecular weight of the polymer and the configuration of the copolymer can be freely designed.

For the polymer containing an unmodified cyclic monomer used in the present invention, in order to control the molecular weight of the polymer or in order to obtain a polymer in the form of a star polymer, the configuration may be designed so that a plurality of polymer chain ends are bonded together using a conventional at least bifunctional coupling agent such as dimethyldichlorosilane, methyltrichlorosilane, dimethyldibromosilane, methyltribulorobromsilane, titanocene dichloride, dichloromethane, dibromomethane, chloroform, carbon tetrachloride, silicon tetrachloride, iron tetrachloride, tin tetrachloride, epoxidized soybean oil, or an ester.

When the polymer containing an unmodified cyclic monomer used in the present invention is a block copolymer, the block copolymer may contain a plurality of polymer blocks. Examples of the polymer block contained in the block copolymer include a polymer block composed of only monomer units derived from at least one cyclic olefin monomer, a polymer block composed of only monomer units derived from at least one cyclic conjugated diene monomer, a polymer block composed of monomer units derived from at least one cyclic olefin monomer and at least one comonomer copolymerizable with the cyclic olefin monomer, a polymer block composed of monomer units derived from at least one cyclic conjugated diene monomer and at least one comonomer copolymerizable with the cyclic conjugated diene monomer, a polymer block composed of monomer units derived from at least one cyclic olefin monomer, at least one cyclic conjugated diene monomer and at least one comonomer copolymerizable with these monomers, and a polymer block composed only of monomer units derived from at least one comonomer copolymerizable with the cyclic conjugated diene monomer. For many purposes, a variety of polymer blocks can be designed and produced by polymerization. By appropriately selecting and combining these polymer blocks, a block copolymer having an unmodified cyclic monomer unit suitable for the intended use can be obtained.

When a part or the whole of the polymer block containing an unmodified cyclic monomer unit used in the present invention is composed of a cycloolefin monomer unit, a cyclic conjugated diene monomer unit, or both of these monomer units, it is recommended that the polymer block contains a continuous arrangement of at least 10 such monomer units, preferably 20 or more such monomer units, more preferably 30 or more such monomer units, from the viewpoint of obtaining a block copolymer having excellent thermal and mechanical properties.

As a method forproducing the block copolymer containing an unmodified cyclic monomer unit used in the present invention, there can be mentioned, for example, a method comprising: preparing various types of block unit polymers, that is, a block unit polymer composed of only monomer units derived from at least one cyclic conjugated diene monomer, a block unit polymer composed of at least one cyclic conjugated diene monomer and at least one comonomer-derived monomer copolymerizable with the cyclic conjugated diene monomer, and a block unit polymer composed of only monomer units derived from at least one comonomer copolymerizable with the cyclic conjugated diene monomer; selecting a suitable combination of these block unit polymers; combinations of polymer-linked block unit polymers; if necessary, the resulting block copolymer containing cyclic monomer units is hydrogenated.

Specific examples of preferred modes of the method for producing the block copolymer include the following modes.

One version of the method includes the following forming steps: polymerizing a polymer comprising block units derived from at least one cyclic conjugated diene monomer, or block units derived from only cyclic conjugated diene monomers; polymerizing the block unit polymer with at least one comonomer copolymerizable with the cyclic conjugated diene monomer, wherein the comonomer is sequentially bonded to one or both ends of the block unit polymer by polymerization; if necessary, the resulting block copolymer is hydrogenated.

Another mode of the method comprises the steps of: polymerizing at least one comonomer copolymerizable with the cyclic conjugated diene monomer to obtain a block unit polymer; polymerizing a block unit polymer with at least one cyclic conjugated diene monomer and optionally at least one comonomer copolymerizable with the cyclic conjugated diene monomer, wherein the cyclic conjugated diene monomer and the optional comonomer aresequentially bonded to one or both ends of the block unit polymer by polymerization; if necessary, the resulting block copolymer is hydrogenated.

Yet another form of the method includes the forming steps of: polymerizing a block unit polymer comprising a monomer unit derived from at least one cyclic conjugated diene monomer, or a block unit polymer consisting of only monomer units derived from a cyclic conjugated diene monomer; polymerizing the block unit polymer with at least one comonomer copolymerizable with the cyclic conjugated diene monomer to obtain a polymer; then, sequentially bonding a block unit polymer comprising a monomer unit derived from at least one cyclic conjugated diene monomer or a block unit polymer composed of only monomer units derived from cyclic conjugated diene monomers to the polymer by polymerization; if necessary, the resulting block copolymer is hydrogenated.

Yet another mode of the method comprises the steps of: polymerizing at least one comonomer copolymerizable with the cyclic conjugated diene monomer to obtain a block unit polymer; polymerizing a block unit polymer with a block unit polymer containing a monomer unit derived from at least one cyclic conjugated diene monomer or a block unit polymer composed of only a monomer unit derived from a cyclic conjugated diene monomer; at least one comonomer copolymerizable with the cyclic conjugated diene monomer is sequentially bonded to the resulting polymer by polymerization, and the resulting block copolymer is hydrogenated, if necessary.

Yet another form of the method includes the forming steps of: polymerizing a block unit polymer comprising a monomer unit derived from at least one cyclic conjugated diene monomer or a block unit polymer composed of only monomer units derived from a cyclic conjugated diene monomer; polymerizing the block unit polymer with at least one comonomer copolymerizable with the cyclicconjugated diene monomer to obtain a polymer; the molecular chain ends of the polymer are bonded using a conventional at least difunctional coupling agent (e.g., dimethyldichlorosilane, methyltrichlorosilane, dimethyldibromosilane, methyltribulorobromosilane, titanocene dichloride, methylene chloride, methylene bromide, chloroform, carbon tetrachloride, silicon tetrachloride, titanium tetrachloride, tin tetrachloride, epoxidized soybean oil, or an ester), and the resulting block copolymer is hydrogenated, if necessary.

Yet another form of the method includes the forming steps of: the polymerization contains at least oneMonomer units derived from cyclic conjugated diene monomersA block unit polymer of a unit or a block unit polymer composed of only monomer units derived from a cyclic conjugated diene monomer; using end group modifiers (ethylene oxide, propylene oxide, hexane oxide, CO)₂Acid chloride, etc.) to introduce a functional group to one or both ends of the block unit polymer to obtain a functional block unit polymer; if desired, hydrogenating the resulting functional block copolymer; and bonding the non-hydrogenated or hydrogenated functional block unit polymer to other functional polymers having functional groups capable of bonding to the functional groups of the functional block unit polymer.

Yet another form of the method includes the forming steps of: polymerizing a block unit polymer comprising a monomer unit derived from at least one cyclic conjugated diene monomer or a block unit polymer composed of only monomer units derived from a cyclic conjugated diene monomer; polymerizing the block unit polymer with at least one comonomer copolymerizable with the cyclic conjugated diene monomer to obtain a polymer; using end group modifiers (ethylene oxide, propylene oxide, hexane oxide, CO)₂Acid chloride, etc.) to introduce a functional group to one or both ends of the polymer thus obtained to obtain a functional polymer; if desired, subjecting the functional polymer to a hydrogenation reaction; and bonding the non-hydrogenated or hydrogenated functional block unit polymer to other functional polymers having functional groups capable of bonding to the functional groups of the functional block unit polymer.

Another mode of the process comprises polymerizing at least one cyclic conjugated diene monomer with at least one comonomer copolymerizable with the cyclic conjugated diene monomer, wherein the at least one comonomer has a different polymerization rate than the cyclic conjugated diene monomer, thereby obtaining a trapezoidal (taper) block copolymer; if desired, the resulting ladder block copolymer is hydrogenated.

Another aspect of the process includes polymerizing a cyclic conjugated diene monomer and at least one comonomer copolymerizable therewith, wherein the ratio of the cyclic conjugated diene monomer to the at least one comonomer is not an integer; if desired, the block copolymer is hydrogenated.

Yet another form of the method includes the forming steps of: polymerizing a block unit polymer composed of monomer units (derived from a cyclic conjugated diene monomer), wherein the polymerization is carried out until a desired specific conversion is achieved; polymerizing the block unit polymer with at least one comonomer copolymerizable with the cyclic conjugated diene monomer at a polymerization rate different from that of the cyclic conjugated diene monomer to obtain a block copolymer; if necessary, the resulting block copolymer is hydrogenated.

In the present invention, the block unit polymer composed of at least one cyclic olefin monomer unit, at least one cyclic conjugated diene monomer unit, or both monomer units may further include a monomer unit derived from at least one comonomer copolymerizable with the cyclic conjugated diene monomer or cyclic olefin monomer.

Further, in the present invention, the block unit polymer composed of at least one monomer unit derived from a comonomer copolymerizable with the cyclic conjugated diene monomer may further include at least one monomer unit selected from the group consisting of cycloolefin monomer units and cyclic conjugated diene monomer units.

In the present invention, as for the polymer block comprising at least one cycloolefin monomer unit, it is most preferable to use a polymer block comprising or consisting of a monomer unit containing a cyclohexane ring.

As the polymer block comprising cyclic conjugated diene monomer units, it is most preferable to use a polymer block comprising or consisting of cyclohexene ring-containing monomer units.

In the present invention, in order to obtain an unmodified cyclic conjugated diene block copolymer or a modified cyclic conjugated diene block copolymer used as a thermoplastic elastomer or a particularly transparent resin having impact resistance, the block copolymer needs to be composed of at least two agglomerated phases (block units) and at least one elastomer phase (block unit), and these two phases constitute a domain structure.

In the polymer molecular chain of such a block copolymer, the agglomerated phase functions as a physical crosslinking site at a temperature lower than Tg, and as a result, the block copolymer has elasticity (rubber elasticity). On the other hand, at a temperature of Tg or higher, the agglomerated phase becomes fluid, and thus the block copolymer is imparted with fluidity. Therefore, in this case, injection molding becomes possible. In addition, the block copolymer can be used as a reusable material.

In the present invention, when an optimum polymerization method,i.e., living anionic polymerization, is employed, a cyclic conjugated diene block copolymer comprising at least two block units each composed mainly of a cyclic conjugated diene monomer or a derivative thereof or composed of a cyclic conjugated diene monomer and a vinyl aromatic monomer (hereinafter often referred to as "X block"), and at least one block unit composed mainly of a chain conjugated diene monomer or a derivative thereof (hereinafter often referred to as "Y block") can be obtained. Then, by subjecting the resulting block copolymer to hydrogenation reaction, a block copolymer having cycloolefin monomer units can be obtained.

For example, as a modified block copolymer having elasticity (rubber elasticity), such as a thermoplastic elastomer or a particularly transparent resin having impact resistance, a linear block copolymer represented respectively by formula (6) and a radial block copolymer represented respectively by formula (7) can be produced:

(X-Y)_l，X-(Y-X)_m，Y-(X-Y)_n(6) wherein each of l and n is independently an integer of 2 or more, and m is an integer of 1 or more; and

[(Y-X)_n]_m+2Z，[(X-Y)_n]_m+2Z，[(Y-X)_n-Y]_m+2Z，

[(X-Y)_n-X]_m+2z (7) wherein m is an integer of 0 or more, and n is an integer of 1 or more; and each z independently represents the residue of a polyfunctional coupling agent, such as dimethyldichlorosilane, dichloromethane, silicon tetrachloride, tin tetrachloride or epoxidized soybean oil, or the residue of a polymerization initiator, such as a polyfunctional organometallic compound containing a metal of group IA of the periodic Table.

There is no particular limitation on the polymerization method for producing the unmodified cyclic monomer unit-containing polymer to be used in the present invention, and any conventional polymerization method (for example, radical polymerization, anion polymerization, cation polymerization, ring-opening polymerization, polycondensation, addition polymerization or coordination polymerization) may be employed as long as an unmodified polymer satisfying the requirements of the present invention can be obtained. However, the most preferable polymerization method for obtaining a polymer containing an unmodified cyclic monomer unit is a living anionic polymerization method using a complex composed of at least one organometallic lithium compound containing a metal belonging to group IA (group IA metal) and at least one complexing agent (preferably an amine) as a polymerization catalyst to obtain a polymer containing an unmodified cyclic monomer unit. The obtained polymer is hydrogenated, if necessary. In this way, a polymer containing unmodified cyclic monomer units having the desired molecular weight and the desired polymer structure can be obtained.

Examples of group IA metals used in the preferred polymerization process of the present invention include lithium, sodium, potassium, rubidium, cesium and francium. Among them, lithium, sodium and potassium are preferable. Among them, lithium is particularly preferable.

In the present invention, as described above, the complex used as a polymerization catalyst for polymerization is a complex of at least one organometallic compound containing a group IA metal and at least one complexing agent.

Preferred examples of the complex include complexes of organolithium compounds, organosodium compounds or organopotassium compounds.

The most preferred complexes are those of organolithium compounds.

The organolithium compound preferably used in the polymerization catalyst used in the above polymerization method is a compound containingat least one lithium atom bonded to an organic molecule containing at least one carbon atom or an organic polymer.

An example of such an organic molecule is C₁-C₂₀Alkyl radical, C₂-C₂₀Unsaturated aliphatic hydrocarbon group, C₅-C₂₀Aryl radical, C₃-C₂₀Cycloalkyl and C₄-C₂₀A cycloalkadienyl group.

Examples of the organolithium compound which can be used in the polymerization process of the present invention include methyllithium, ethyllithium, n-propyllithium, isopropyllithium, n-butyllithium, sec-butyllithium, tert-butyllithium, pentyllithium, hexyllithium, aryllithium, cyclohexyllithium, phenyllithium, hexamethylenedilithium, cyclopentadienyllithium, indenyllithium, butadienyldilithium and isoprenyldilithium. In addition, oligomeric or polymeric organolithium compounds containing lithium atoms in their polymer molecular chains, respectively, such as polybutadienyllithium, polyisoprenyllithium and polystyryllithium, can also be used.

There is no particular limitation on the kind of the preferred organolithium compound as long as it can form a stable complex (compound). However, representative examples of such organolithium compounds include methyllithium, ethyllithium, n-propyllithium, isopropyllithium, n-butyllithium, sec-butyllithium, tert-butyllithium, and cyclohexyllithium.

Among these, n-butyllithium (n-BuLi) is most preferable from the commercial viewpoint.

The organometallic compounds containing a group IA metal which can be used in the above polymerization process may be used alone or in admixture as desired.

As catalysts for the above polymerization processes, the most preferred complexing agents for forming complexes of organometallic compounds containing group IA metals are one or more amines.

Examples of amines useful as complexing agents include those containing at least one R¹R²N-radical (wherein R¹And R²Each independently an alkyl group, an aryl group or a hydrogen atom) or an organic polymer amine, R above¹R²The N-group is a polar group having a non-covalent electron pair capable of coordinating with an organometallic compound of a group IA metal to form a complex.

Among these amines, tertiary amines are most preferred.

Preferred examples of the tertiary amine used in the present invention are trimethylamine, triethylamine, dimethylaniline, diethylaniline, tetramethyldiaminomethane, tetramethylethylenediamine, tetramethyl-1, 3-propanediamine, tetramethyl-1, 3-butanediamine, tetramethyl-1, 4-butanediamine, tetramethyl-1, 6-hexanediamine, tetramethyl-1, 4-phenylenediamine, tetramethyl-1, 8-naphthalenediamine, tetramethylbenzidine, tetraethylethylenediamine, tetraethyl-1, 3-propanediamine, tetramethyldiethylenetriamine, tetraethyldiethylenetriamine, pentamethyldiethylenetriamine, pentaethyldiethylenetriamine, diazabicyclo [ 2.2.2]octane, 1, 5-diazabicyclo [ 4.3.0]-5-nonene, 1, 8-diazabicyclo [ 5.4.0]-7-undecene, 1, 4, 8, 11-tetramethyl-1, 4, 8, 11-tetraazacyclotetradecane, tetrakis (dimethylamino) ethylene, tetraethyl-2-butylene-1, 4-diamine, and hexamethyl phosphoramide (HMPT).

Examples of the most preferred amines include Tetramethylmethylenediamine (TMMDA), Tetraethylmethylenediamine (TEMDA), Tetramethylethylenediamine (TMEDA), Tetraethylethylenediamine (TEEDA), Tetramethylpropylenediamine (TMPDA), Tetraethylpropylenediamine (TEPDA), Tetramethylbutylenediamine (TMBDA), Tetraethylbutylenediamine (TEBDA), tetramethylpentylenediamine, Tetraethylpentylenediamine (TEHDA), Tetraethylhexylenediamine (TMHDA), Tetraethylhexyldiamine (TEHDA) and diazabicyclo- [ 2.2.2]octane (DABCO).

Tetramethylethylenediamine (TMEDA) is a particularly preferred example of a complexing agent useful in the present invention from a commercial standpoint.

The above amine complexing agents may be used alone or in combination.

For the polymerization catalyst used for the preparation of the cyclic conjugated diene polymer by the above-mentioned optimum polymerization method (i.e., living anion polymerization method), which is prepared from an organometallic compound containing at least one group IA metal (group IA metal) and at least one complexing agent, it is desirable that the catalyst is a catalyst prepared from n-butyllithium (n-BuLi) and at least one amine selected from Tetramethylmethylenediamine (TMMDA), Tetramethylethylenediamine (TMEDA), Tetramethylpropylenediamine (TMPDA) and diazabicyclo [ 2.2.2]octane (DABCD).

From a commercial standpoint, the most preferred catalyst is one prepared from n-butyllithium (n-BuLi) and Tetramethylethylenediamine (TMEDA).

In the above-mentioned most preferred polymerization method, it is preferred that the complex is prepared by reacting an organometallic compound containing a group IA metal with at least one amine (complexing agent) prior to the polymerization reaction, and the resulting complex is used as a polymerization catalyst.

In the present invention, there is no particular limitation on the method for preparing the complex (polymerization catalyst). If desired, the preparation can be carried out by conventional methods.

Examples of such conventional methods include a method of dissolving an organometallic compound containing a group IA metal in an organic solvent under a dry inert atmosphere and adding a solution of a complexingagent (amine); and a method of dissolving the complexing agent (amine) in an organic solvent under a dry inert atmosphere and adding thereto a solution of an organometallic compound containing a group IA metal. From these methods, a preferred method can be appropriately selected.

Preferably, the above organic solvent is appropriately selected depending on the type and amount of the organometallic compound and the type and amount of the complexing agent (amine), and sufficiently degassed and dried before use.

The reaction to obtain the complex of at least one organometallic compound with at least one complexing agent (amine) is generally carried out at from-100 ℃ to 100 ℃.

Examples of inert gases used to prepare the complexes include helium, nitrogen and argon. Among them, nitrogen and argon are preferred from a commercial viewpoint.

In the preparation of a complex composed of a group IA-containing organometallic compound and an amine (complexing agent), which is used in the above-mentioned optimum polymerization method for producing a cyclic conjugated diene polymer, it is preferable to use the following molar ratio of amine to group IA metal contained in the organometallic compound. The molar ratio is:

in general: A/B =1, 000/1-1/1, 000

Preferably: A/B = 500/1-1/500

More preferably: A/B = 100/1-1/100

Further preferably: A/B = 50/1-1/50

Most preferably: a/B = 20/1-1/20 wherein a is the molar amount of amine (amine compound molecule) and B is the molar amount of group ia metal contained in the organometallic compound. When the above molar ratio A/B is within the range defined above, a stable complex can be obtained in high yield, advantageously used for producing a cyclic conjugated diene polymer having a narrow molecular weight distribution.

When the molar ratio A/B falls outside the range defined above, there are likely to occur many disadvantages that the production process of the complex becomes costly and the complex becomes unstable, so that undesirable side reactions such as transfer reaction and group IA metal hydride removal reaction are likely to occur simultaneously with the polymerization reaction.

As described above, the most preferable method for producing the cyclic conjugated diene polymer is a living anion polymerization method using the complex as a polymerization catalyst.

The polymerization method used in the present invention is not particularly limited, and may be carried out by vapor phase polymerization, bulk polymerization, or solution polymerization.

The polymerization reaction may be carried out in a batch, semi-batch or continuous manner.

Examples of the polymerization solvent used for the solution polymerization are aliphatic hydrocarbons such as butane, n-pentane, n-hexane, n-heptane, n-octane, isooctane, n-nonane and n-decane; alicyclic hydrocarbons such as cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, ethylcyclohexane, cycloheptane, cyclooctane, decalin and norbornane; aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene and cumene; and ethers such as diethyl ether and tetrahydrofuran.

These polymerization solvents may be used alone or in combination, if necessary.

Preferred polymerization solvents are aliphatic, cycloaliphatic and aromatic hydrocarbons. More preferred polymerization solvents are aliphatic hydrocarbons, cycloaliphatic hydrocarbons and mixtures thereof. The most preferred polymerization solvents are n-hexane, cyclohexane and mixtures thereof.

In the polymerization process for producing the cyclic conjugated diene, the amount of the polymerization catalyst to be used is not particularly limited and may vary depending on the intended use of the polymer to be used. However, the polymerization catalyst is generally used in an amount of 1X 10 moles per mole of the metal atom of the monomer^-6mol-1×10^-1mol, preferably 5X 10^-6mol-5×10^-2mol。

In the polymerization method, the polymerization reaction temperature may be appropriately selected. However, the polymerization temperature is generally-100 ℃ to 150 ℃, preferably-80 ℃ to 120 ℃, more preferably-30 ℃ to 110 ℃, most preferably 0 ℃ to 100 ℃. From a commercial point of view, polymerization temperatures of from room temperature to 90 ℃ are advantageous.

In the polymerization method of the present invention, the polymerization reaction time is not particularly limited and may vary depending on the intended use of the polymer and other polymerization reaction conditions. However, the polymerization time is generally not more than 48 hours, preferably 1 to 10 hours.

In the polymerization method, the polymerization reaction is preferably carried out in an inert atmosphere such as nitrogen, argon or helium. It is particularly preferred that these inert gases are used after they have been completely dried.

There is no particular limitation on the pressure in the polymerization reaction system. A wide range of pressures may be selected so long as the pressure is sufficient to maintain the monomers and solvent in the liquid state at the polymerization temperature in the above range. Furthermore, care must be taken to prevent impurities such as water, oxygen and carbon dioxide from invading the polymerization system to deactivate the polymerization catalyst or to form the living end of the polymer.

In the polymerization process, the polymerization catalysts may be used alone or in admixture.

In the polymerization method, when a predetermined degree of polymerization is reached, a usual additive may be added to the polymerization reaction system. Examples of such commonly used additives are terminal modifiers such as halogen gas, carbon dioxide, carbon monoxide, alkylene oxide, alkylene sulfide, isocyanate compound, imino compound, aldehyde compound, ketone compound, thione compound, ester, lactone, amide group-containing compound, urea compound or acid anhydride; terminal branching agents, such as polyepoxides, polyisocyanates, polyimines, polyaldehydes, polyanhydrides, polyesters, polyhalides, or metal halides; coupling agents, such as dimethyldichlorosilane, methyltrichlorosilane, dimethyldibromosilane, methyltrobromosilane, titanocene dichloride, zirconocene dichloride, methylene chloride, methylene bromide, chloroform, carbon tetrachloride, silicon tetrachloride, titanium tetrachloride, tin tetrachloride, epoxidized soybean oil or esters; a polymerization terminator; polymeric stabilizers, and stabilizing agents such as heat stabilizers, antioxidants, or ultraviolet light absorbers.

In the polymerization process of the present invention, conventional heat stabilizers, antioxidants and ultraviolet light absorbers may be used.

For example, phenols, organophosphates, organophosphonites, organic amines and organic sulfur heat stabilizers, antioxidants and ultraviolet light absorbers can be used.

Each of the heat stabilizer, the antioxidant and the ultraviolet absorber is generally added in an amount of 0.001 to 10 parts by weight per 100 parts by weight of the cyclic conjugated diene polymer.

As the polymerization terminator, any conventional polymerization terminator can be used as long as it can deactivate the polymerization activator of the polymerization catalyst of the present invention. Preferred examples of the polymerization terminator include water, C₁-C₁₀Alcohols, ketones, polyols (such as ethylene glycol, propylene glycol or glycerol), phenols, carboxylic acids, and halogenated hydrocarbons.

The polymerization terminator to be added is generally used in an amount of 0.001 to 10 parts by weight per 100 parts by weight of the polymer containing cyclic monomer units. The polymerization terminator may be added before or simultaneously with the addition of the heat stabilizer, antioxidant and/or ultraviolet light absorber. Alternatively, the living end of the polymer may be deactivated by contacting the living end group with molecular hydrogen.

Most preferably, the modified cyclic monomer unit-containing polymer of the present invention is obtained by a process which comprises polymerizing a cyclic conjugated diene monomer to obtain a polymer containing a cyclic conjugated diene monomer unit, and if necessary, subjecting the resulting polymer to hydrogenation to hydrogenate unsaturated carbon-carbon bonds in the polymer.

One example of the most preferable method for obtaining a polymer containing an unmodified cyclic monomer unit (hydrogenated polymer) includes polymerizing a cyclic conjugated diene monomer to obtain a polymer, and hydrogenating the obtained polymer in the presence of a hydrogenation catalyst to hydrogenate part or all of unsaturated carbon-carbon bonds contained in the cyclic conjugated diene polymer.

In this case, after the polymerization reaction for obtaining the cyclic conjugated diene polymer reaches a predetermined polymerization degree, the cyclic conjugated diene polymer is hydrogenated to obtain a desiredhydrogenated polymer.

For the hydrogenation, the following methods can be used:

a batch process comprising deactivating a polymerization catalyst to terminate the polymerization reaction, adding a hydrogenation catalyst to the same reactor as that used for the polymerization reaction and introducing hydrogen into the reactor to obtain a hydrogenated polymer;

a semi-batch process comprising deactivating a polymerization catalyst to terminate the polymerization reaction to obtain a polymer solution, transferring the obtained polymer solution to a reactor different from a reactor used for the polymerization reaction, adding a hydrogenation catalyst to the reactor, and introducing hydrogen into the reactor to obtain a hydrogenated polymer; and

a continuous process comprising continuously conducting a polymerization reaction and a hydrogenation reaction in a tubular reactor to obtain a hydrogenated polymer.

From the above methods, a desired method can be appropriately selected.

As described above, the hydrogenation reaction of the cyclic conjugated diene polymer is carried out in the presence of a hydrogenation catalyst in a hydrogen atmosphere.

In more detail, the hydrogenation is generally carried out as follows: the polymer solution is maintained at a predetermined temperature under an atmosphere of hydrogen or an inert gas, and a hydrogenation catalyst is added to the polymer solution with or without stirring, and hydrogen is introduced into the reaction system until a predetermined pressure level is reached.

The hydrogenation reaction may be carried out in a conventional manner, i.e. batch, semi-batch or continuous. These means may be used alone or in combination.

The type and amount of the hydrogenation catalyst used in the present invention are not particularly limited as long as the catalyst used can provide a degree of hydrogenation so as to introduce the desired amount of unsaturated cyclic molecular units. However, it is preferred that the hydrogenation catalyst used in the present invention is a homogeneous hydrogenation catalyst (organometallic compound or complex) or a heterogeneous hydrogenation catalyst (solid catalyst) containing at least one metal selected from the group consisting of metals of groups IVA to VIII of the periodic Table of the elements and rare earth metals.

Most preferably, the hydrogenation catalyst is a homogeneous hydrogenation catalyst, i.e., an organometallic compound or complex containing at least one metal selected from the group consisting of group IVA to VIII metals and rare earth metals.

These organometallic compounds or complexes as hydrogenation catalysts can be supported on inorganic compounds, such as silica or zeolites, or organic polymers, such as crosslinked polystyrene.

Examples of the metal contained in the hydrogenation catalyst used in the present invention include titanium, zirconium, hafnium, chromium, molybdenum, tungsten, manganese, rhenium, iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium, platinum, lanthanum, cerium, praseodymium, niobium, palladium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, yttrium, and lutetium. Among them, preferred are titanium, zirconium, hafnium, rhenium, cobalt, nickel, ruthenium, rhodium, palladium, cerium, niobium, samarium, europium, gadolinium and yttrium.

Particularly preferred are titanium, cobalt, nickel, ruthenium, rhodium and palladium.

To obtain a homogeneous hydrogenation catalyst using an organometallic compound or complex containing the above-mentioned metals, it is required that a ligand such as hydrogen, halogen, nitrogen compound or organic compound be coordinated or bonded to these metals. These ligands may be used alone or in combination. When these ligands are used in admixture, it is preferred to select an appropriate ligand mixture so that the resulting organometallic compound or complex becomes soluble in the solvent used.

Examples of ligands are hydrogen; fluorine; chlorine; bromine; nitric oxide; carbon monoxide; organic compounds containing a functional group such as a hydroxyl group, an ether group, an amine group, a thiol group, a phosphine group, a carbonyl group, an olefin group or a diene group, or non-polar organic compounds containing no functional group.

Examples of the organic ligand include aldehydes such as salicylaldehyde, 2-hydroxy-1-naphthaldehyde and 2-hydroxy-3-naphthaldehyde; hydroxybenzophenones, such as 2 ' -hydroxyacetophenone, 2 ' -hydroxybutyrylphenone and 2 ' -hydroxypropionylphenone; diketones, e.g. acetylacetone, benzeneFormylacetone, propionylacetone, isobutyrylacetone, valerylacetone and ethylacetoacetone; carboxylic acids, e.g. isovaleric, caproic, caprylic, lauric, myristic, palmitic, stearic, isostearic, oleic, linoleic, cyclopentanecarboxylic, naphthenic, ethylhexanoic, pivalic, Versatic (containing C)₁₀Synthetic acids of mixtures of monocarboxylic acid isomers, Shell Chemical Co., manufactured and sold), phenylacetic acid, benzoic acid, 2-Naphthoic acid, maleic acid, succinic acid, hexanethioic acid, 2-dimethylbutane thiosulfuric acid, decane thiosulfuric acid, and thiobenzoic acid; organic phosphoric acids, such as dibutyl phosphate, dipentyl phosphate, dihexyl phosphate, diheptyl phosphate, dioctyl phosphate, bis (2-ethylhexyl) phosphate, bis (1-methylheptyl) phosphate, dilauryl phosphate, dioleyl phosphate, diphenyl phosphate, bis (p-nonylphenyl) phosphate, bis [ polyethylene glycol-p-nonylphenyl]phosphate, butyl (2-ethylhexyl) phosphate, 1-methylheptyl (2-ethylheptyl) phosphate, 2-ethylhexyl (p-nonylphenyl) phosphate, 2-ethylhexyl monobutyl phosphonate, 2-ethylhexyl mono-2-ethylhexyl phosphonate, mono-2-ethylhexyl phenylphosphonate, mono-p-nonylphenyl 2-ethylhexyl phosphonate, mono-2-ethylhexyl phosphonate, di-heptyl phosphate, dioctyl phosphate, bis (2-ethylhexyl) phosphate, bis (1-methylheptyl) phosphate, dioleyl phosphate, bis (p-nonylphen, Phosphonic acid mono-1-methylheptyl ester, phosphonic acid mono-p-nonylphenyl ester, dibutylphosphinic acid, bis (2-ethylhexyl) phosphinic acid, bis (1-methylheptyl) phosphinic acid, dilaurylphosphinic acid, dioleylphosphinic acid, diphenylphosphinic acid, bis (p-nonylphenyl) phosphinic acid, butyl (2-ethylhexyl) phosphinic acid, (2-ethylhexyl) (1-methylheptyl) phosphinic acid, (2-ethylhexyl) (p-nonylphenyl) phosphinic acid, butylphosphinic acid, 2-ethylhexyl phosphinic acid, 1-methylheptylphosphinic acid, oleylphosphinic acid, laurylphosphinic acid, phenylphosphinic acid and p-nonylphenylphosphinic acid; alcohols, phenols and thiols, e.g. ethanol, n-propanol, isopropanol, tert-butanol, tert-amyl alcohol, n-hexanol, cyclohexanol, allyl alcohol, 2-butenol, 3-hexenol, 2, 5-decadienol, benzyl alcohol, phenol, catechol, 1-naphthol, 2, 6-di-tert-butylphenol, 2, 6-di-tert-butyl-4-methylphenol, 2, 4, 6-tri-tert-butylphenol, 4-phenylphenol, ethanethiol, 1-butanethiol, 2-pentanethiol, 2-isobutanethiol, thioPhenol substitutes, 2-naphthalene thiol, cyclohexane thiol, 3-methylcyclohexane thiol, 2-naphthalene thiol, phenylmethane thiol, and 2-naphthalene methane thiol; acetylacetone, tetrahydrofuran, diethyl ether, dimethyl sulfoxide, pyridine, ethylenediamine, dimethylformamide, triphenylphosphine, cyclopentadienyl, substituted cyclopentadienyl, indenyl, fluorenyl, pi-allyl, substituted allyl, cyclooctadieneyl, methyl, ethyl, butyl, phenyl and tolyl.

These ligands may be used alone or in combination. When these ligands are used in admixture, it is particularly preferred to select a suitable combination of ligands so that the resulting organometallic compound or complex becomes soluble in the solvent used.

The various hydrogenation catalysts may be used alone or in combination as desired.

Furthermore, it is most preferred from a commercial standpoint to use as the hydrogenation catalyst a combination of an organometallic compound or complex comprising at least one component selected from the group consisting of group IVA to VIII metals and rare earth metals and an organometallic compound of at least one metal selected from the group consisting of group IA to IIA metals and group IIIB metals, such as alkyllithium, alkylmagnesium and alkylaluminum.

Specific examples of the organometallic compound containing a metal selected from group IA-IIA metals and group IIIB metals include alkyllithium such as methyllithium, ethyllithium, n-propyllithium, isopropyllithium, n-butyllithium, sec-butyllithium, t-butyllithium, pentyllithium, hexyllithium, phenyllithium or cyclopentadienyllithium; alkyl magnesium, such as dimethyl magnesium, diethyl magnesium or dibutyl magnesium; and alkylaluminum such as trimethylaluminum, triethylaluminum, triisopropylaluminum, tributylaluminum, triisobutylaluminum, trihexylaluminum, tricyclohexylaluminum, diethylaluminum hydride, diisobutylaluminum hydride, methylaluminoxane or ethylaluminoxane. These organometallic compounds may be used alone or in admixture thereof.

In the present invention, when the polymer containing an unmodified cyclic monomer unit is a hydrogenated polymer, the amount of the hydrogenation catalyst to be used for the hydrogenation reaction can be appropriately determined depending on the kind of the polymer to be hydrogenated (e.g., main chain structure and molecular weight) or the hydrogenation reaction conditions (e.g., solvent, temperature, concentration, and solution viscosity). However, the hydrogenation catalyst is generally used in an amount of 0.1 to 100,000 ppm, preferably 1 to 50,000 ppm, more preferably 5 to 10,000 ppm, most preferably 10 to 10,000 ppm, in terms of the concentration of metal atoms, based on the total amount of the polymer to be hydrogenated.

When the amount of the hydrogenation catalyst is extremely low, a satisfactory hydrogenation reaction rate is not obtained. When the amount of the hydrogenation catalyst used is too large, the hydrogenation reaction rate becomes high, and the use of too large an amount of the hydrogenation catalyst is disadvantageous from the economical viewpoint. In addition, when the amount of the hydrogenation catalyst used is too large, it becomes difficult to separate and recover the hydrogenation catalyst, resulting in undesirable results such as adverse effects of the residual catalyst on the polymer.

In the present invention, it is preferred that the solvent used for the hydrogenation reaction is inert to the hydrogenation catalyst and sufficiently dissolves the polymer to be hydrogenated and the hydrogenation catalyst therein.

Examples of the solvent used for the hydrogenation reaction include aliphatic hydrocarbons such as n-pentane, n-hexane, n-heptane, n-octane, isooctane, n-nonane and n-decane; alicyclic hydrocarbons such as cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, cycloheptane, cyclooctane, decalin and norbornane; aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene and cumene; halogenated hydrocarbons such as dichloromethane, dichloroethane, chlorobenzene, dichlorobenzene and trichlorobenzene; and ethers such as diethyl ether, diglyme, triglyme and tetrahydrofuran. These solvents may be used alone or in combination. The solvent issuitably selected depending on the nature of the polymer to be hydrogenated or the hydrogenation reaction conditions.

From a commercial point of view, it is preferable to select the solvent for the hydrogenation reaction from aliphatic hydrocarbons, alicyclic hydrocarbons and aromatic hydrocarbons. The most preferred solvents are aliphatic hydrocarbons, cycloaliphatic hydrocarbons and mixtures of these solvents.

In the present invention, it is commercially advantageous to continuously carry out the polymerization reaction and the hydrogenation reaction. Therefore, it is preferable that the solvent used for the hydrogenation reaction is the same as the solvent used for the polymerization reaction.

In the present invention, the concentration of the polymer solution to be subjected to hydrogenation is not particularly limited. However, the concentration of the polymer solution is preferably 1-90 wt.%, more preferably 2-60 wt.%, most preferably 5-40 wt.%.

When the polymer concentration of the polymer solution is lower than the above range, the hydrogenation operation becomes inefficient and is disadvantageous from an economical point of view. On the other hand, when the concentration of the polymer solution is higher than the above range, the viscosity of the polymer solution becomes high, resulting in a decrease in the reaction rate.

In the present invention, the hydrogenation reaction temperature may be appropriately selected, but is generally from-78 ℃ to 500 ℃, preferably from-10 ℃ to 300 ℃, and more preferably from 20 ℃ to 250 ℃.

When the reaction temperature is lower than the above range, a satisfactorily high reaction rate is not obtained. On the other hand, when the reaction temperature is higher than the above range, many inconveniences are likely to be caused, not only the hydrogenation catalyst is deactivated, but also the polymer is deteriorated.

The pressure of the hydrogenation reaction system is generally in the range of 0.1 to 500 kg/cm²G, preferably 1 to 400 kg/cm²G, more preferably 2 to 300 kg/cm²G。

When the pressure of the hydrogenation reaction system is lower than the above range, a satisfactorily high reaction rate is not obtained. When the pressure is higher than the above range, the reaction rate becomes high, but it is required to use an expensive pressure-resistant reaction apparatus, which is not economical. In addition, such high pressures can cause hydrocracking of the polymer during the hydrogenation reaction.

The hydrogenation reaction time is not particularly limited and may vary depending on the kind and amount of the hydrogenation catalyst, the concentration of the polymer solution, and the temperature and pressure of the reaction system. However, the hydrogenation reaction time is generally 5 minutes to 240 hours.

If desired, after the completion of the hydrogenation reaction, the hydrogenation catalyst can be recovered from the resulting hydrogenation reaction mixture by a conventional method, for example, separating the catalyst by adsorption with an adsorbent, or washing off the catalyst with water or a lower alcohol in the presence of an organic acid and/or an inorganic acid.

The separation and recovery of the hydrogenated cyclic conjugated diene polymer from the hydrogenation reaction mixture can be carried out by conventional methods which are generally used for recovering conventional polymers from the hydrogenation reaction mixture.

Examples of such conventional methods include a steam coagulation method comprising bringing a hydrogenation reaction mixture into direct contact with steam; a method comprising adding a poor solvent for the polymer to the hydrogenation reaction mixture to precipitate the polymer; a method comprising heating the polymerization reaction mixture in a hydrogenation reactor to distill off the solvent; and a method comprising extruding the hydrogenation reaction mixture with an extruder having pores while evaporating the solvent through the pores, thereby obtaining a pelletized polymer. The most suitable method can be selected depending on the solvent used and the nature of the cyclic conjugated diene polymer to be hydrogenated.

When the polymer containing an unmodified cyclic monomer unit of the present invention has a carbon-carbon unsaturated bond, an addition reaction other than hydrogenation may be carried out on the carbon-carbon unsaturated bond, if necessary, using conventional techniques.

For example, the above addition reaction which is not hydrogenated can be carried out by adding at least one substituent to the polymer containing an unmodified cyclic monomer unit using a conventional active agent. Examples of substituents (substituent class 1) include chlorine, e.g. iodine or bromine, C₁-C₂₀Alkyl radical, C₂-C₂₀Unsaturated aliphatic hydrocarbon group, C₅-C₂₀Aryl radical, C₃-C₂₀Cycloalkyl radical, C₄-C₂₀Cycloalkadienyl groups, and 5-to 10-membered heterocyclic groups containing at least one heteroatom selected from nitrogen, oxygen and sulfur. Examples of the other substituents (substituent group 2) include a hydroxyl group, a thiol group, a thiocyano group, an ester group, an ether group (derived from an epoxy group or the like), a thioether group, a thiocarboxylic acid group, a formyl group, a carboxyl group, a carbonyl group, an amino group, an imino group, a phosphonous group, an isocyanato group, a sulfonic acid group, a phosphoric acid group, a phosphonic acid group, a phosphinic acid group and a silyl group. Further examples of substituents (substituent group 3) include hydrocarbon groups having at least one of substituent groups of group 2 selected from C₁-C₂₀Alkyl radical, C₂-C₂₀Unsaturated aliphatic hydrocarbon group, C₅-C₂₀Aryl radical, C₃-C₂₀Cycloalkyl and C₄-C₂₀A cycloalkadienyl group, and a 5-to 10-membered heterocyclic group having at least one substituent of the 2-type substituents, the heterocyclic group containing at least one heteroatom selected from nitrogen, hydrogen, and sulfur.

The modified cyclic monomer unit-containing polymer used in the present invention is represented by the following formula (1'):wherein A-F and a-F are defined by formula (1).

As described above, in formula (1'), each S — X (which is a modifying group and may be the same or different) is independently a functional group containing at least one member selected from the group consisting of oxygen, nitrogen, sulfur, silicon, phosphorus and halogens (including fluorine, chlorine, bromine and iodine) or a residue of an organic compound containing the functional group.

Furthermore, in formula (1'), S-X are each a weight percentage of the modifying group S-X, based on the weight of the polymer, and satisfy the following requirements:

0<s + t + u + v + w + x<100, and

0≤s，t，u，v，w，x＜100．

for the addition reaction method of bonding the functional group or the residue of the organic compound having the functional group to the polymer containing a cyclic monomer unit of the raw material for the modified polymer of the present invention,any conventional method may be employed, wherein the polymer containing a cyclic monomer unit to be subjected to the addition reaction may be in the form of a polymer solution, a molten polymer or a solid polymer. Examples of such methods are: a method comprising bonding the functional group or the residue of the organic compound containing the functional group to a polymer containing cyclic monomer units by an ethylenic reaction; a method comprising bonding the functional group or the residue of the organic compound containing the functional group to a polymer containing cyclic monomer units by radical reaction in the presence or absence of a radical initiator; and a method comprising forming a polymer having a cyclic monomer unit having a living end by, for example, living anionic polymerization, and bonding the functional group or an organic compound having the functional group to one or both living ends of the polymer. The preferred method can be appropriately selected from these methods.

In the present invention, the content of the functional group or the residue of the organic compound containing the functional group in the modified cyclic monomer unit-containing polymer is generally 0.001 wt.% to less than 100 wt.%, preferably 0.005 wt.% to 80 wt.%, more preferably 0.01 wt.% to 50 wt.%, particularly preferably 0.05 wt.% to 40 wt.%. Furthermore, most preferably 0.1 wt.% to 20 wt.%.

Examples of the functional group used for bonding the polymer containing the cyclic monomer or the functional group contained in the residue of the organic compound include a hydroxyl group, an ether group, an epoxy group, a carboxylic acid group, an ester group, a carboxylate group, an acid anhydride group, an acid halide group, an aldehyde group, a carbonyl group, an amino group, an amide group, an imide group, an imino group, an oxazoline group, a hydrazine group, a hydrazide group, an amidino group, a nitrile group, a nitro group, anisocyano group, a cyanato group, an isocyano group, a silyl ester group, a silyl ether group, a silanol group, a thiol group, a thioether group, a thiocarboxylic acid group, a sulfo group, a sulfinic acid group, a sulfenic acid group, a thiocyanate group, an isothiocyanate group, a thioether group, phosphoric acid, phosphonic acid.

Particularly preferred examples of the functional group bonded to the polymer containing the cyclic monomer or the functional group contained in the residue of the organic compound include a hydroxyl group, an epoxy group, a carboxylic acid group, an ester group, a carboxylate group, an acid anhydride group, an amino group, an amide group, an imino group, an oxazoline group, a hydrazine group, a hydrazide group, an isocyanide group, a silyl ester group, a silyl ether group, a silanol group, a thiol group, a thioether group, a thiocarboxylic acid group and a sulfonic acid group. These functional groups or organic chemical residues containing these functional groups may be used alone or in combination.

Representative examples of organic compounds which contain at least one modifying group selected from a functional group and a residue of an organic compound containing the functional group and are useful for bonding the at least one modifying group to the cyclic monomer-containing unit by an addition reaction include acrylic acid, methacrylic acid, metal salts of acrylic acid, metal salts of methacrylic acid, methyl acrylate, methyl methacrylate, ethyl acrylate, maleic acid, dimethyl maleate, diethyl maleate, succinic acid, dimethyl fumarate, diethyl fumarate, itaconic acid, citraconic acid, Hi-micic acid, citraconic acid, mesaconic acid, sorbic acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, endo-cis-bicyclo [ 2, 2, 1]hept-5-ene-2, 3-dicarboxylic acid, methylbicyclo [ 2], 2, 1]hept-5-ene-2, 3-dicarboxylic acid, maleic anhydride, trimellitic anhydride, 1, 2, 4, 5-pyromellitic anhydride, succinic anhydride, itaconic anhydride, citraconic anhydride, Hi-mic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, maleimide, succinimide, phthalimide, glycidyl methacrylate, glycidyl acrylate, glycidyl maleate, glycidyl succinate, glycidyl fumarate, glycidyl terephthalate, styrene-p-glycidyl ether; 3, 4-epoxy-1-butene; 3, 4-epoxy-1-butene; 3, 4-epoxy-3-methyl-1-butene; 3, 4-epoxy-1-pentene; 3, 4-epoxy-3-methyl-1-pentene and 5, 6-epoxy-1-heptene, vinylalkoxysilane (examples of alkoxy moiety include methoxy, ethoxy and butoxy), epoxyalkoxysilane (examples of alkoxy moiety include methoxy, ethoxy and butoxy), aminoalkoxysilane (examples of alkoxy moiety include methoxy, ethoxy and butoxy), diisocyanate compound and oxazoline compound.

In the present invention, maleic anhydride and glycidyl methacrylate are most preferable among organic compounds which contain at least one modifying group selected from a functional group and a residue of an organic compound containing the functional group and which can be used for bonding the at least one modifying group to a polymer containing a cyclic monomer unit by an addition reaction from a commercial viewpoint.

The above organic compounds may be used alone or in combination.

As described above, the resin composition of the present invention comprises (α) at least one polymer selected from the group consisting of a polymer containing an unmodified cyclic monomer unit represented by formula (1) and a polymer containing a modified cyclic monomer unit represented by formula (1'), and (β) at least one polymer other than polymer (α), wherein the content of polymer (α) is at least 1wt.%, based on the total weight of polymer (α) and polymer (β), and the number average molecular weight of polymer (α) is 10,000 to 5,000,000.

In the resin composition of the present invention, when the weight of the polymer (β 1) and the weight of the polymer (β 0) are respectively represented by β 2 and β 3 based on the total weight of the polymer (α) and the polymer (β), the polymer (β 4) and the polymer (β 6) are generally used in a weight ratio (expressed as a weight ratio of the polymer (α)) satisfying the requirements of 1. ltoreq. β 5/(β 7+ β 9)<100, preferably 1<β 8/(α + β)<100, more preferably 2. ltoreq. α 0/(α + β)<99, further preferably 5. ltoreq. α/(α + β)<95.

When the resin composition is used as an industrial material, it most preferably satisfies the requirement of 10. ltoreq. α/(α + β). ltoreq.90.

When the amount ratio of the polymer (α) to the total amount of the polymer (α) and the polymer (β) is outside the range defined above, a resin composition satisfactorily improved in mechanical properties cannot be obtained.

In the resin composition of the present invention, the polymer (β) may be a commonly used thermoplastic resin or a commonly used curable resin, preferably a thermoplastic resin.

Examples of the thermoplastic resin used as the polymer (β) include olefin polymers, styrene polymers, conjugated diene polymers, halogenated conjugated diene polymers, (meth) acrylate polymers, (meth) acrylonitrile copolymers, halogenated vinyl polymers, ester polymers, ether polymers, amide polymers, imide polymers, thioether polymers, sulfone polymers and ketone polymers.

Examples of the curable resin used as the polymer (β) include unsaturated polyester resins, urea resins, melamine resins, polyurethane resins, and phenol resins.

As the polymer (β) in the resin composition of the present invention, the above thermoplastic resin and curable resin may be used alone or in the form of a mixture thereof.

Specific examples of the polymer (β) include olefin polymers such as Polyethylene (PE), copolymers of ethylene with norbornene or derivatives thereof, ethylene-propylene copolymers such as EP or EP rubbers, ethylene-propylene-diene copolymers (EPDM), polybutylene-1, polypentene-1, polyhexene-1, polyoctene-1, polyisobutylene, polymethyl-1-butene and poly 4-methyl-1-pentene, styrene polymers such as polystyrene (PSt), syndiotactic polystyrene (s-PST), styrene-acrylic acid copolymers, styrene-maleic anhydride copolymers (SMA), ABS resins and AES resins, conjugated diene polymers such as poly (PBd), polyisoprene (PIp), block, graft, ladder or random configuration conjugated diene copolymers [ e.g., butadiene-isoprene copolymers, styrene-butadiene copolymers (e.g., SB or SBS), propylene-butadiene copolymers, styrene-isoprene copolymers (e.g., SI or SIS), α -methylstyrene-butadiene copolymers, α -methylstyrene-isoprene copolymers, styrene-butadiene copolymers (e.g., SB or SBS), propylene-butadiene copolymers, styrene-isoprene copolymers (e.g., SI or SIS), styrene-isoprene copolymers (PA) and Poly (PA) copolymers such as styrene-isoprene copolymers, poly (PA-formaldehyde), poly (PA-methyl methacrylate copolymers, poly (PA-styrene-methyl methacrylate), poly (PA-methyl methacrylate) copolymers, poly (PA-styrene-methyl methacrylate copolymers, poly (PA-styrene-methyl methacrylate), poly (PA-styrene-co-styrene-co-styrene-co-styrene-co-butadiene), poly (PA-co-styrene-butadiene), poly (PA-styrene-co-styrene-co-butadiene), poly (ABS), poly (PA-styrene-co-styrene-butadiene), poly (styrene-co-butadiene) (e.g., styrene-co-styrene-co-butadiene) (e.g.g., styrene-co-styrene-ethylene-styrene-co-styrene-co-isoprene-styrene-co-ethylene-styrene-ethylene-butadiene) (e.g., styrene-butadiene-styrene-co-butadiene-styrene-ethylene-styrene-ethylene-styrene-co-styrene-co-styrene-ethylene-.

These polymers may be used alone or in combination.

Particularly preferred examples of the thermoplastic resin include olefin polymers, styrene polymers, conjugated diene polymers, hydrogenated conjugated diene polymers, ester polymers, ether polymers, amido polymers and thioether polymers.

In the present invention, the most preferable polymer (β) to be used together with the polymer (α) (i.e., the polymer containing an unmodified cyclic monomer unit and/or the modified conjugated diene polymer) to obtain the resin composition of the present invention is an olefin polymer or an amido polymer.

As the olefin polymer used as the polymer (β), it is preferable that the olefin polymer has an intrinsic viscosity of 0.1 to 100 (L/g), more preferably 0.5 to 50 (L/g), most preferably 1 to 10 (L/g), as measured in decalin at 130 ℃.

Among the olefin polymers having an intrinsic viscosity value within the above range, crystalline polyolefins are preferred. Polyethylene (PE), polypropylene (PP) are particularly preferred.

Specific examples of PE and PP are High Density Polyethylene (HDPE), Medium Density Polyethylene (MDPE), Low Density Polyethylene (LDPE), Linear Low Density Polyethylene (LLDPE), ethylene-propylene copolymer (EP) and propylene-1-butene copolymer.

These crystalline polyolefins have a crystallinity of 30% or more, preferably 50% or more, and more preferably 70% or more, as measured by X-ray diffraction.

On the other hand, for the amido polymer used as polymer (β), it is stated that 9 ℃ is at 25 ℃6％H₂SO₄Preferably, the intrinsic viscosity [ η]is measured at 0.1 to 100 (L/g), more preferably 0.5 to 50 (L/g), most preferably 1 to 10 (L/g).

Among the amide polymers having intrinsic viscosity values in the above range, crystalline polyamides are preferred. Specific examples of the crystalline polyamide include crystalline polyamides obtained by polymerizing at least one member selected from the group consisting of a reaction product of a diamine and a dicarboxylic acid, a lactam and an amino acid.

Preferred examples of the crystalline polyamide include aliphatic polyamides such as nylon 6, nylon 6.66, nylon 11, nylon 12, nylon 46, nylon 66, nylon 610, nylon 612, nylon 1212; semi-aromatic polyamides, such as nylon 4 T.4I (T: terephthalic acid, I: isophthalic acid), nylon 6.6T, nylon 66.6T, nylon 6I, nylon 6 T.6I, nylon MXD6 (MXD: m-tolylenediamine); and copolymers or polymer blends of these aliphatic polyamides and semi-aromatic polyamides.

In order to stabilize the morphology of the resin composition of the present invention, it is preferable that the resin composition contains, as the polymer (α), a polymer containing a modified cyclic monomer unit having at least one functional group selected from a hydroxyl group, an epoxy group, a carboxylic acid group, an ester group, a carboxylate group, an acid anhydride group, an amino group, an amide group, an imide group, an imino group, an oxazoline group, an isocyano group, a cyanato group, an isocyano group, a silyl ester group, a silyl ether group, a silanol group, a thiol group, a thioether group, a thiocarboxylic acid group and a sulfonic acid group and/or an organic compound residue containing the functional group, and as the polymer (β), a polymer having a covalent bond with the functional group of the above-mentioned polymer (α), and as a result, a reaction product of the polymer (α) and the polymer (β).

Examples of the polyester (β) having a functional group capable of forming a covalent bond with the polymer (α) include an ester polymer (having an ester group and may further have another functional group such as a hydroxyl group and a carboxyl group), an ether polymer (having an ether group and may further have another functional group such as a hydroxyl group), an amide polymer (having an amide group and may further have another functional group such as an amino group and a carboxyl group), and a thioether polymer (having a thioether group and may further have another functional group such as a thiol group).

Further examples of the functional polymer (β) having a functional group capable of forming a covalent bond with the functional group of the polymer (α) include modified polymers (selected from modified olefin polymers, modified styrene polymers, modified conjugated diene polymers, modified hydrogenated conjugated diene polymers, modified ether polymers and modified thioether polymers) having at least one functional group selected from hydroxyl groups, epoxy groups, carboxylic acid groups, ester groups, carboxylic acid ester groups, acid anhydride groups, amino groups, amide groups, imide groups, imino groups, oxazoline groups, isocyano groups, cyanato groups, isocyanato groups, silyl ester groups, silyl ether groups, silanol groups, thiol groups, thioether groups, thiocarboxylic acid groups and sulfonic acid groups, or organic compound residues having the above-mentioned functional groups.

The content of the reaction product of polymer (α) and polymer (β) in the resin composition is generally 0.001 to 100 wt.%, preferably 0.005 to 90 wt.%, more preferably 0.01 to 70 wt.%, based on the weight of the resin composition, and most preferably 0.01 to 50 wt.% in order to simultaneously obtain the stability, mechanical properties and molding processability (flowability) of the resin composition.

The resin composition of the present invention may be obtained by mixing (alloying or blending using conventional techniques) polymer (α), i.e. at least one polymer selected from the group consisting of polymers containing unmodified cyclic monomer units and polymers containing modified cyclic monomer units, with at least one polymer (β), i.e. at least one polymer other than polymer (α).

Examples of the method for blending the polymer (α) and the polymer (β) include a method comprising blending the polymers using a single solvent solution and another method comprising melt-blending the polymers using an extruder, kneader, Banbury mixer or the like.

In producing the resin composition of the present invention, various conventional additives or reinforcing materials to be added to or blended with conventional polymer materials can be used in ordinary amounts for producing conventional resin compositions from the intended use of the resin composition to be produced. Examples of such additives and reinforcing materials include stabilizers such as heat stabilizers, antioxidants and ultraviolet absorbers, lubricants, nucleophiles, plasticizers, colorants, pigments, crosslinking agents, foaming agents, antistatic agents, anti-slip agents, anti-adhesion agents, tackifiers, mold release agents, organic reinforcing materials (e.g., aramids, polyamides, polybenzoxazole and polybenzothiazole), and inorganic reinforcing materials (e.g., short glass fibers, long glass fibers, glass wool, fulling glass fibers, glass beads, glass spheres, carbon fibers, metal fibers, mineral fibers such as asbestos, ceramic fibers or titanium whiskers, and inorganic fillers such as talc, mica, woklulon, kaolin or montmorillonite).

The resin composition of the present invention is advantageously used as an excellent industrial material in various fields such as automobile parts, electronic and electric appliance parts, rail parts, aerospace parts, clothing materials, medical device parts, pharmaceutical and food packaging materials, and general miscellaneous goods materials. In these fields, the resin composition of the present invention is useful as a material for plastics, elastomers, fibers, sheets, films, machine parts, containers, packaging materials, tires and bolts, insulating materials and adhesives.

The present invention is described in more detail with reference to the following reference examples, examples and comparative examples, which are not intended to limit the scope of the present invention.

In the reference example, as the chemical, a substance having the highest purity among commercially available substances was used. In the case of solvents, commercially available solvents are treated by conventional methods prior to use. That is, the solvent is degassed, dehydrated by reflux over the activated metal in an inert gas atmosphere, and purified by distillation.

The number average molecular weight (Mn) and weight average molecular weight (Mw) were determined using calibration curves obtained with reference to standard polystyrene samples using G, P.C (gel permeation chromatography).

(method of measuring Properties of resin composition)

(1) Tensile test (1/8 inches):

tensile Strength (TS), tensile length (TE) and Tensile Modulus (TM) of 1/8-inch thick specimens of the resin composition were measured according to ASTM D638.

(2) Bending test (1/8 inches):

flexural strength (PS) and Flexural Modulus (FM) of a 1/8-inch thick specimen of the resin composition were measured in accordance with ASTM D790.

(3) Izod impact test:

izod impact strength was measured according to ASTM D256 (room temperature).

(4) Heat distortion temperature (HDT:. degree.C.):

the heat set temperature of the resin composition was measured under a load of 1.82 MPa (high load) and a load of 0.45 MPa (low load) in accordance with ASTM D648.

In the above measurements, the following are noted:

1MPa=10．20kg·f／cm²(ii) a And

1J／m=0．102kg·cm／cm)．

reference example 1

(preparation of polymerization catalyst 1)

Under a dry argon atmosphere, a predetermined amount of Tetramethylethylenediamine (TMEDA) was dissolved in a mixed solvent of cyclohexane and n-hexane (cyclohexane/n-hexane ratio: 9/1 (V/V)). The resulting solution was cooled and maintained at-10 ℃. Then, a solution of n-butyllithium (n-Bu-Li) in n-hexane was gradually added to the solution of TMEDA in cyclohexane/n-hexane in an amount such as to give a TMEDA/n-butyllithium molar ratio of 1/4 under a dry argon atmosphere, thereby obtaining a polymerization catalyst 1 (a complex of TMEDA with n-BuLi).

[ production of Polymer 1]

A fully dried 5 liter autoclave with an electromagnetic induction stirrer was purged with dry nitrogen using conventional methods.

2,800 g of cyclohexane and 400g of 1, 3-cyclohexadiene were introduced into the autoclave. Polymerization catalyst 1 (a complex of TMEDA with n-BuLi) is shown in the amount of lithium atoms as 10. An amount of 50mol was added to the autoclave. The polymerization was carried out at 30 ℃ for 8 hours. After this period, 1-heptanol was added to the resulting reaction mixture to terminate the polymerization reaction.

A stabilizer [ Irganox B215(0037HX), commercially available from CIBA GEIGY, Switzerland]was added to the reaction mixture, and then the solvent was removed by a conventional method to obtain a cyclohexadiene homopolymer.

The number average molecular weight (Mn) of the resulting homopolymer was 49,000. The molecular weight distribution (Mw/Mn) was 1.19.

The glass transition temperature (Tg) of the homopolymer was 120 ℃. Tensile Modulus (TM) was 4, 250MPa as determined by ASTM D638.

In a 30mm phi twin-screw extruder (PCM 30 manufactured by Ikegai, Japan) having an L/D ratio of 17, 100 parts by weight of a cyclohexadiene homopolymer, 3 parts by weight of maleic anhydride and 1 part by weight of Parhexa25B manufactured by Nippon Oil and falls, Japan (280 ℃ C.) were mixed and then extruded. The resulting extrudate was pelletized to obtain the desired product (polymer 1).

The resulting polymer 1 was subjected to extraction using hot acetone to remove unreacted maleic anhydride, and then dried in vacuo at 80 ℃. The amount of maleic anhydride grafted on the cyclohexadiene homopolymer was determined by sodium methoxide titration. As a result, it was found that the amount of maleic anhydride grafted on the cyclohexadiene homopolymer was 0.4 mol%.

Reference example 2

[ production of Polymer 2]

2,800 g of cyclohexane and 400g of 1, 3-cyclohexadiene were introduced into the autoclave. Then, the polymerization catalyst (a complex of TMEDA and n-BuLi) obtained in the same manner as in reference example 1 was charged into the autoclave in an amount of 10.50 mol in terms of the amount of lithium atom. The polymerization was carried out at 30 ℃ for 8 hours to obtain a cyclohexadiene homopolymer. After this period, 1-heptanol was added to the resulting reaction mixture to terminate the polymerization reaction.

Adding to the reaction mixture the amount of cobalt atoms, based on the weight of the polymerRepresents 100ppm of cobalt triacetylacetonate [ Co (acac)]₃Hydrogenation catalyst [ Co (acac)]with Triisobutylaluminum (TIBAL)₃Molar ratio of (c)/(TIBAL): 1/6].

The autoclave was purged with hydrogen. The temperature in the autoclave rose to 185 ℃. At 50 kg/cm²Hydrogenation was carried out under G hydrogen pressure for 4 hours.

After the hydrogenation reaction was completed, the autoclave was cooled to room temperature, and the pressure in the autoclave was reduced to atmospheric pressure. The autoclave was purged with nitrogen and the resulting reaction mixture was treated with methanol using conventional techniques.

A stabilizer [ Irganox B215(0037HX), commercially available from CIBA GEIGY, Switzerland]was added to the reaction mixture, and then the solvent was removed by a conventional method to obtain a hydrogenated cyclohexadiene homopolymer.

¹The H-NMR measurement showed that the degree of hydrogenation of cyclohexene rings in the polymer chain structure of the cyclohexadiene homopolymer was 100 ml%. The hydrogenated cyclohexadiene homopolymer had a weight average molecular weight (Mn) of 50, 700. The hydrogenated cyclohexadiene homopolymer had a molecular weight distribution (Mw/Mn) of 1.15.

The glass transition temperature (Tg) of the homopolymer was 221 ℃. The tensile modulus was 6, 520MPa according to ASTM D638.

In a 30mm phi twin-screw extruder (PCM 30 manufactured by Ikegai, Japan) having an L/D ratio of 17, 100 parts by weight of a hydrogenated cyclohexadiene homopolymer, 3 parts by weight of maleic anhydride and 1 part by weight of Parhexa25B manufactured by Nippon Oil and falls, Japan (280 ℃ C.) were mixed and then extruded. The resulting extrudate was pelletized to obtain the desired product (polymer 2).

The resulting polymer 2 was extracted using hot acetone to remove unreacted maleic anhydride, and then dried in vacuo at 80 ℃. The amount of maleic anhydride grafted on the cyclohexadiene homopolymer was determined by sodium methoxide titration. As a result, it was found that the amount of maleic anhydride grafted on the hydrogenated cyclohexadiene homopolymer was 0.2 mol%.

Reference example 3

[ production of Polymer 3]

2,800 g of cyclohexane and 60g of 1, 3-cyclohexadiene were introduced into the autoclave. The polymerization catalyst (a complex of TMEDA and n-BuLi) obtained in the same manner as in reference example 1 was charged into the autoclave in an amount of 10.50 mol in terms of the amount of lithium atom. The polymerization was carried out at 30 ℃ for 4 hours to obtain a cyclohexadiene homopolymer. Thereafter, 280g of butadiene was charged into the autoclave, and polymerization was further carried out at 45 ℃ for 1 hour to obtain a cyclohexadiene-butadiene diblock copolymer. To the resulting reaction mixture was added 60g of 1, 3-cyclohexadiene. The polymerization was carried out at 30 ℃ for 4 hours to obtain a cyclohexadiene-butadiene triblock copolymer.

After this period, 1-heptanol was added to the resulting reaction mixture to terminate the polymerization reaction.

To the reaction mixture was added a hydrogenation catalyst composed of titanocene and n-BuLi in an amount of 250ppm in terms of the amount of titanium atom based on the weight of the polymer (titanocene/n-BuLi molar ratio: 1/1). The autoclave was purged with hydrogen. The temperature in the autoclave rose to 75 ℃. At 10 kg/cm²Hydrogenation was carried out under G hydrogen pressure for 4 hours.

A stabilizer [ Irganox B215(0037HX), marketed by CIBA GEIGY, Switzerland]was added to the reaction mixture, followed by removal of the solvent by a conventional method, to thereby obtain a hydrogenated cyclohexadiene-butadiene triblock copolymer (polymer 3) exhibiting rubber elasticity.

¹The H-NMR measurement showed that the degree of hydrogenation of the cyclohexadiene polymer block was 0 mol%. The degree of hydrogenation was 100 mol% for the 1, 2-vinyl bond segment and the 1, 4-bond segment of the butadiene polymer block. The number average molecular weight (Mn) of the resulting hydrogenated triblock copolymer was 96, 500. The molecular weight distribution (Mw/Mn) was 1.09.

The Tensile Strength (TS) of the copolymer was 16.80 MPa. The tensile length (TE) was 750%.

Reference example 4

[ production of Polymer 4]

2,800 g of cyclohexane and 60g of 1, 3-cyclohexadiene were introduced into the autoclave. The polymerization catalyst (a complex of TMEDA and n-BuLi) obtained in the same manner as in reference example 1 was charged into the autoclave in an amount of 15.50 mol in terms of the amount of lithium atom. The polymerization was carried out at 30 ℃ for 4 hours to obtain a cyclohexadiene homopolymer. Thereafter, 280g of butadiene was charged into an autoclave, and polymerization was further carried out at 60 ℃ for 60 minutes to obtain a cyclohexadiene-butadiene diblock copolymer. To the resulting reaction mixture was added 60g of 1, 3-cyclohexadiene. The polymerization was carried out at 30 ℃ for 5 hours, thereby obtaining a cyclohexadiene-butadiene triblock copolymer.

A hydrogenation catalyst consisting of ferrocene xylene and n-BuLi in an amount of 100ppm in terms of the amount of titanium atom, based on the weight of the polymer, was added to the reaction mixture (molar ratio titanocene/n-BuLi 1/1). The autoclave was purged with hydrogen. The temperature in the autoclave rose to 75 ℃. At 10 kg/cm²Hydrogenation was carried out for 30 minutes under G hydrogen pressure.

To the reaction mixture was added Irganox B215(0037HX) (available from CI-BA GEIGY, Switzerland) as a stabilizer, followed by removing the solvent by a conventional method, to thereby obtain a hydrogenated cyclohexadiene-butadiene triblock copolymer (Polymer 4) having rubber elasticity.

¹The H-NMR measurement showed that the degree of hydrogenation of the cyclohexadiene polymer block was 0mol percent. The degree of hydrogenation was 100 mol% for the 1, 2-vinyl bond segment and the 1, 4-bond segment of the butadiene polymer block. Number average molecular weight of the resulting hydrogenated triblock copolymerIs 77 and 600. Molecular weight distributionIs 1.12.

The Tensile Strength (TS) of the copolymer was 27.50 MPa. The stretched length (TE) was 600%.

Reference example 5

In a 30mm phi twin-screw extruder (PCM 30 manufactured by Ikegai, Japan) having an L/D ratio of 17, 100 parts by weight of the polymer 3 (hydrogenated cyclohexene-butadiene triblock copolymer) obtained in referential example 3, 2 parts by weight of maleic anhydride and 0.5 part by weight of Parhexa25B manufactured by Nippon Oil and falls, Japan (280 ℃ C.) were mixed and extruded at 300 ℃. The resulting extrudate was pelletized, thereby obtaining the desired product (polymer 5).

The resulting polymer 5 was subjected to extraction using hot acetone to remove unreacted maleic anhydride, and then dried in vacuo at 80 ℃. The amount of maleic anhydride grafted on the hydrogenated cyclohexadiene-butadiene triblock copolymer was determined by sodium methoxide titration. As a result, it was found that the amount of maleic anhydride grafted on the hydrogenated cyclohexadiene-butadiene triblock copolymer was 1.2 mol%.

Reference example 6

In a 30mm phi twin-screw extruder (PCM 30 manufactured by Ikegai, Japan) having an L/D ratio of 17, 100 parts by weight of the polymer (4) (hydrogenated cyclohexadiene-butadiene triblock copolymer) obtained in referential example 4, 2 parts by weight of maleic anhydride and 0.5 part by weight of Parhexa25B manufactured by Nippon Oil and falls, Japan (280 ℃ C.) were mixed and extruded at 300 ℃. The resulting extrudate was pelletized to obtain the desired product (polymer 6).

The resulting polymer 6 was subjected to extraction using hot acetone to remove unreacted maleic anhydride, and then dried under vacuum at 80 ℃. The amount of maleic anhydride grafted on the hydrogenated cyclohexadiene-butadiene triblock copolymer was determined by sodium methoxide titration. As a result, it was found that the amount of maleic anhydride grafted on the hydrogenated cyclohexadiene-butadiene triblock copolymer was 1.4 mol%.

Example 1

70 parts by weight of nylon 66 (Leona, manufactured by Asahi Chemical Industry Co., Ltd., Japan) was dry-blended and mixed at 250-280 ℃ in a 30mm phi twin-screw extruder (PCM-30, manufactured by Ikegai, Japan) having an L/D ratio of 17^R1402S) and 30 parts by weight of polymer 1, and then extruded. The obtained extrudate was pelletized, thereby obtaining a resin composition. The obtained resin composition was injection-molded at 280 ℃ to obtain a resin composition sample.

The obtained resin composition sample had a Tensile Strength (TS) of 79.5 MPa, a tensile length (TE) of 6%, a Flexural Strength (FS) of 121.6 MPa, a Flexural Modulus (FM) of 3, 037MPa, an Izod impact strength (Izod) of 36.7J/m, and a Heat Distortion Temperature (HDT) of 92 ℃ measured under a high load.

Example 2

70 parts by weight of nylon 66 (Leona, manufactured by Asahi Chemical Industry Co., Ltd., Japan) was dry-blended and mixed at 250-280 ℃ in a 30mm phi twin-screw extruder (PCM 30, manufactured by Ikegai, Japan) having an L/D ratio of 17^R1402S) and 30 parts by weight of polymer 2, and then extruded. The obtained extrudate was pelletized, thereby obtaining a resin composition. The obtained resin composition was injection-molded at 295 ℃ to obtain a resin composition sample.

The obtained resin composition sample had a Tensile Strength (TS) of 83.3 MPa, a tensile length (TE) of 5%, a Flexural Strength (FS) of 125.5 MPa, a Flexural Modulus (FM) of 3, 325MPa, an Izod impact strength (Izod) of 33.8J/m, and a Heat Distortion Temperature (HDT) of 148 ℃ measured under a high load.

Example 3

70 parts by weight of polypropylene (Asahi Chemical Industry Polypropylene M1500, manufactured and sold by Asahi Chemical Industry Co., Ltd., Japan) was dry-blended and mixed at 200-240 ℃ in a 30 mm.phi.twin-screw extruder (PCM 30, manufactured and sold by Ikegai, Japan) having an L/D ratio of 17^R) And 30 parts by weight of polymer 3, followed by extrusion. Granulating the obtained extrudate to obtainA resin composition. The obtained resin composition was injection-molded at 230 ℃ to obtain a resin composition sample.

The obtained resin composition sample had a Tensile Strength (TS) of 22.5 MPa, a tensile length (TE) of 500% or more, a Flexural Strength (FS) of 27.4 MPa, a Flexural Modulus (FM) of 853MPa, an Izod impact strength (Izod) of 716J/m, and a Heat Distortion Temperature (HDT) of 82 ℃ measured under a low load.

Comparative example 1

The same polypropylene product as used in the production of the resin composition of example 3 was provided to evaluate its properties, and the properties were measured under the same conditions as in example 3. The Tensile Strength (TS) was 30.2 MPa, the tensile length (TE) was 500% or more, the flexural strength (TS) was 41.6 MPa, the Flexural Modulus (FM) was 1, 245, the Izod impact strength (Izod) was 12.7J/m, and the Heat Distortion Temperature (HDT) under low load was 68 ℃.

Examples 4 and 5

In each of examples 4 and 5, substantially the same procedureas in example 3 was repeated except that the amounts of polypropylene and polymer 3 were changed.

Table 1 shows the results of the measurements carried out in examples 3 to 5, and the results of the measurements carried out in comparative example 1.

TABLE 1

	Amount ratio of PP/Polymer 3	TS	FM	Izod
Example 3	70/30	22.5	853	716
Example 4	85/25	24.8	907	706
Example 5	80/20	25.9	986	695
Comparative example 1	PP=100	30.2	1245	12.7

Example 6

70 parts by weight of polypropylene (Asahi Chemical Industry Polypropylene M1500, manufactured and sold by Asahi Chemical Industry Co., Ltd., Japan) was dry-blended and mixed at 200-240 ℃ in a 30 mm.phi.twin-screw extruder (PCM 30, manufactured and sold by Ikegai, Japan) having an L/D ratio of 17^R) And 30 parts by weight of polymer 4, followed by extrusion. The obtained extrudate was pelletized, thereby obtaining a resin composition. The obtained resin composition was injection-molded at 230 ℃ to obtain a resin composition sample.

The obtained resin sample had a Tensile Strength (TS) of 29.3 MPa, a tensile length (TE) of 500% or more, a Flexural Strength (FS) of 30.3 MPa, a Flexural Modulus (FM) of 892MPa, an Izod impact strength (Izod) of 704J/m, and a Heat Distortion Temperature (HDT) of 91 ℃ measured under a low load.

Example 7

70 parts by weight of nylon 66 (Leona, manufactured by Asahi Chemical Industry Co., Ltd., Japan) was dry-blended and mixed at 250-280 ℃ in a 30mm phi twin-screw extruder (PCM 30, manufactured by Ikegai, Japan) having an L/D ratio of 17^R1402S) and 30 parts by weight of polymer 5, and then extruded. The obtained extrudate was pelletized, thereby obtaining a resin composition. The obtained resin composition was injection-molded at 280 ℃ to obtain a resin composition sample.

For the obtained resin composition sample, the Tensile Strength (TS) was 60.5 MPa, the tensile length (TE) was 67%, the Flexural Strength (FS) was 67.6 MPa, the Flexural Modulus (FM) was 1, 840MPa, the Izod impact strength (Izod) was N.B. (not broken), and the Heat Distortion Temperature (HDT) measured under high load was 62 ℃.

Comparative example 2

The same nylon 66 product as used in the production of the resin composition of example 7 was provided to evaluate its properties, and the properties were measured under the same conditions as in example 7. The Tensile Strength (TS) was 79.4 MPa, the tensile length (TE) was 60%, the flexural strength (TS) was 107.8 MPa, the Flexural Modulus (FM) was 2, 843, the Izod impact strength (Izod) was 44.1J/m, and the Heat Distortion Temperature (HDT) under high load was 68 ℃.

Examples 8 and 9

In each of examples 8 and 9, substantially the same procedure as in example 7 was repeated except that the amounts of nylon 66(PA) and polymer 5 were changed.

Table 2 shows the results of the measurements carried out in examples 7 to 9, and the results of the measurements carried out in comparative example 2.

TABLE 2

	Amount ratio of PP/Polymer 5	TS	FM	Izod
Example 7	70/30	60.5	1840	N.B.
Example 8	85/25	61.3	1910	N.B.
Example 9	80/20	64.8	1970	1090
Comparative example 2	PA=100	79.4	2843	44.1

Example 10

70 parts by weight of nylon 66 (Leona, manufactured by Asahi Chemical Industry Co., Ltd., Japan) was dry-blended and mixed at 250-280 ℃ in a 30mm phi twin-screw extruder (PCM-30, manufactured by Ikegai, Japan) having an L/D ratio of 17^_1402S) and 30 parts by weight of a polymer6, and then extruding. The obtained extrudate was pelletized, thereby obtaining a resin composition. The obtained resin composition was injection-molded at 280 ℃ to obtain a resin composition sample.

The obtained resin composition sample had a Tensile Strength (TS) of 61.3 MPa, a tensile length (TE) of 71%, a Flexural Strength (FS) of 68.2 MPa, a Flexural Modulus (FM) of 1, 870MPa, an Izod impact strength (Izod) of 1, 080J/m, and a Heat Distortion Temperature (HDT) of 64 ℃ measured under a high load.

Example 11

70 parts by weight of polyphenylene sulfide (M2588 sold by Toray-Phillips Petroleum Co., Ltd., Japan), 30 parts by weight of Polymer 2, and 0.5 part by weight of gamma-aminopropyltriethoxysilane (A1100 sold by NIPPON U-NICAR, COMPANY, LIMIT-ED Co., Ltd., Japan) were dry-blended and mixed at 300-320 ℃ in a 30mm phi twin-screw extruder (PCM-30 sold by Ikegai Co., Ltd., Japan) having an L/D ratio of 17, followed by extrusion. The obtained extrudate was pelletized, thereby obtaining a resin composition. The obtained resin composition was injection-molded at 310 ℃ to obtain a resin composition sample.

The obtained resin composition sample had a Tensile Strength (TS) of 81.2 MPa, a tensile length (TE) of 7%, a Flexural Strength (FS) of 128.4 MPa, a Flexural Modulus (FM) of 3, 275MPa, an Izod impact strength (Izod) of 41.9J/m, and a Heat Distortion Temperature (HDT) of 179 ℃ when measured under a high load.

Reference example 7

(preparation of polymerization catalyst 2)

Under a dry argon atmosphere, a predetermined amount of Tetramethylethylenediamine (TMEDA) was dissolved in a mixed solvent of cyclohexane and n-hexane (cyclohexane/n-hexane ratio: 9/1 (V/V)). The resulting solution was cooled and maintained at-10 ℃. Then, a solution of n-butyllithium (n-BuLi) in n-hexane is gradually added to the solution of TMEDA in cyclohexane/n-hexane, under a dry argon atmosphere, in an amount such as to provide a TMEDA/n-BuLi molar ratio of 1/1. As a result, polymerization catalyst 2 (a complex of TMEDA and n-BuLi) was obtained.

(production of polymers 7 and 8)

A well dried 100ml Schlenk tube was washed well with dry argon using conventional methods. 3.00 g of 1, 3-cyclohexadiene and 20.0 g of cyclohexane were introduced into a Schlenk tube. While maintaining the temperature of the resulting solution at 25 ℃, a polymerizationcatalyst was added to the solution in an amount of 0.07 mmol in terms of the amount of lithium atom, and the polymerization reaction was carried out for 5 hours under a dry argon atmosphere.

200ml of the reaction mixture was transferred to a 200ml metal autoclave. Adding cobalt triacetylacetonate (Co (acac)₃Hydrogenation catalyst [ Co (acac)]with Triisobutylaluminum (TIBAL)₃Molar ratio of (c)/(TIBAL): 1/6], was added in an amount of 80ppm in terms of the amount of cobalt atoms based on the weight of the polymer.

The autoclave was purged with hydrogen and heated to 185 ℃. The hydrogenation reaction was carried out at 40 kg/cm²G under hydrogen pressure for 4 hours.

To the reaction mixture was added Irganox B215(0037HX) (sold by CI-BA GEIGY, Switzerland) as a stabilizer, followed by removal of the solvent by a conventional method, to obtain a hydrogenated cyclohexadiene homopolymer (Polymer 7).

¹The H-NMR measurement result showed that the degree of hydrogenation of the cyclohexene ring in the polymer chain structure of the cyclohexadiene homopolymer was 100 mol%. That is, the polymer molecular chain structure of the above cyclohexadiene homopolymer is composed of only cyclohexane rings.

Number average molecular weight of the resulting hydrogenated cyclohexadiene homopolymer

Is 43 and 900. Molecular weight distribution

Was 1.08.

4.92 g of Polymer 7 and 5.88 g of maleic anhydride were added to 150ml of 1, 2, 4-Trichlorobenzene (TCB) under a dry nitrogen atmosphere to obtain a mixture. The resulting mixture was heated to 120 ℃ with stirring to completely dissolve the hydrogenated cyclohexadiene homopolymer and maleic anhydride in TCB.

To the resulting solution, 24mmol of benzoyl peroxide and 50% diluted product of dioctyl phthalate (Nyper Bo sold by Nippon Oil&faces Co., Ltd., Japan) were gradually added and reacted at 120 ℃ for 5 hours under a dry nitrogen atmosphere.

After completion of the reaction, the resulting reaction mixture was reprecipitated several times with acetone/TCB to obtain a maleic anhydride-modified hydrogenated cyclohexadiene homopolymer, which was dried under vacuum at 80 ℃ to obtain the desired product (Polymer 8).

The amount of maleic anhydride grafted on the hydrogenated cyclohexadiene homopolymer was determined with sodium methoxide. The amount of maleic anhydride grafted on the hydrogenated cyclohexadiene homopolymer was found to be 1.7 mol%.

Example 12

70 parts by weight of nylon 66 (Leona available from Asahi Chemical Industry Co., Ltd., Japan)^_1300S) and 30 parts by weight of polymer 7 were dry-blended and mixed in a Brabender at 300 c to obtain a resin composition. The resulting resin composition was molded using a compression molding machine heated to 300 ℃. The viscoelastic spectrum of the obtained resin composition was measured. ResultsShown in fig. 2.

Example 13

70 parts by weight of nylon 66 (Leona available from Asahi Chemical Industry Co., Ltd., Japan)^_1300S) and 30 parts by weight of polymer 8 were dry-blended and mixed in a Brabender at 300 c to obtain a resin composition. The resulting resin composition was molded using a compression molding machine heated to 300 ℃. The viscoelastic spectrum of the obtained resin composition was measured. The results are shown in FIG. 3.

With respect to the change in the loss factor (tan. delta.) (dynamic viscoelasticity index) on the high temperature side, it was confirmed that the resin composition of example 13 had a peak at a considerably higher temperature than the resin composition of example 12.

The molecular structure of the polymer (α) selected from the group consisting of a polymer containing an unmodified cyclic monomer unit and a polymer containing a modified cyclic monomer unit, wherein the cyclic monomer unit is derived from a cyclic conjugated diene, contained in the novel resin composition of the present invention can be freely controlled to a large extent, and therefore, by combining the polymer (α) with the polymer (β) which is not the polymer (α), a resin composition excellent in various properties such as thermal stability with respect to rigidity and impact resistance can be freely provided to a large extent (in terms of selection of properties thereof).

The resin composition of the present invention may be mixed with an inorganic reinforcing material, if necessary. The resin composition of the present invention can be advantageously used as an industrial material such as plastics, elastomers, fibers, sheets, films, mechanical parts, containers, packaging materials, tires, bolts, insulating materials, adhesives and the like in various application fields such as in automobile parts (engine covers, cosmetic covers, wheel covers, fenders, dust covers, pots, undercovers, automobile deflectors, carburetors, sealing belts, gears, cams, air caps, tubes, ducts, cooling fans, instrument panels, roofs, interior parts, and the like), electronic and electrical parts (connectors, sockets, substrates, housings such as television housings, telephone housings, transformer housings and computer housings, lenses, organic glass, switching sockets, electric lamp reflectors, bellows, relay boards, feedback transformers and the like), rail parts, aerospace parts, clothing materials, medical equipment parts, the medicine and food includes material, separating membrane, exchange membrane, printed circuit board and common sundries.

Claims

1. A resin composition comprising: (2) at least one polymer selected from the group consisting of a polymer (1) containing an unmodified cyclic monomer unit and a polymer (1 ') containing a modified cyclic monomer unit, the polymer (1) and the polymer (1 ') being represented by the following formulae (1) and (1 '), respectively:

wherein A-C are monomer units constituting the main chain of each of the polymers (1) and (1'), wherein the monomer units A-C are arranged in an arbitrary order, and a-C are the weight percentages of the monomer units A-C based on the total weight of the monomer units A-C, respectively; whereinEach A is a cyclohexene unit, each B is a1, 3-cyclohexadiene unit, and each C is independently selected from the group consisting of 1, 3-hexadiene, isoprene units and 1, 3-pentadiene units, wherein a-C satisfy the following requirements: a + b + c =100, a is greater than or equal to 0, b is less than or equal to 100, c is greater than or equal to 0 and less than 100, and a + b is not equal to 0;wherein each modifying group S-U, which may be the same or different, is independently a residue of an organic compound containing anhydride groups, and wherein S-U is the weight percentage of the modifying groups S-U, respectively, based on the weight of the polymer (1'), and the requirement that 0<S + t + U<100, and 0. ltoreq. S, t,U<100, the number average molecular weight of the polymer (α) is 10,000-5,000,000, 000, with the proviso that a + B =100, a>0 and B>0, or when 0<a + B<100, the polymer (α) is a block copolymer containing at least one polymer block containing at least 10 consecutive arrangements of monomer units selected from A monomer units, B monomer units and both A and B monomer units, and (β) is not polymer (α), being a thermoplastic resin selected from olefin polymers, amide polymers and thioether polymers, the total weight of polymer (α) and polymer (β), the weight content of polymer (α) being at least 6726.6726 wt.%.

2. The resin composition according to claim 1, wherein in at least one of the formulae (1) and (1'), the main chain has a block copolymer configuration in which the block copolymer has at least one polymer block containing at least one monomer unit selected from the group consisting of A monomer units and B monomer units.

3. The resin composition according to claim 1, wherein in at least one of the formulae (1) and (1'), the main chain has a block copolymer configuration in which the block copolymer has at least one polymer block composed of at least one A monomer unit and at least one B monomer unit.

4. The resin composition according to claim 1, wherein in at least one of (1) and (1'), the main chain has a block copolymer configuration in which the block copolymer has at least one polymer block composed of A monomer units.

5. The resin composition according to claim 1, wherein in at least one of (1) and (1'), the main chain has a block copolymer configuration in which the block copolymer has at least one polymer block composed of B monomer units.

6. The resin composition according to claim 1, wherein the thermoplastic resin is an olefin polymer having an intrinsic viscosity of 0.1 to 100 liters/g as measured in decalin at 135 ℃.

7. The resin composition according to claim 1, wherein the thermoplastic resin is 96% H at 25 ℃₂SO₄An amide polymer having an intrinsic viscosity of 0.1 to 100 (liter/g) as measured in (1).

8. The resin composition according to claim 1, wherein the thermoplastic resin is at least one olefin polymer selected from the group consisting of an ethylene homopolymer, an α -olefin homopolymer and a copolymer of ethylene and α -olefin.

9. The resin composition according to claim 1, wherein the thermoplastic resin is a crystalline polyamide obtained by polymerizing at least one member selected from the group consisting of a reaction product of a diamine and a dicarboxylic acid, a lactam and an amino acid.